Nanoparticles compositions containing polymers and anthranilic acid diamide insecticides for propagule coating

ABSTRACT

Disclosed is an insecticidal composition comprising by weight based on the total weight of the composition:
         (a) from about 0.25 to about 25% of one or more anthranilic diamide insecticides;   (b) from about 2.5 to about 25% of a poly(lactic acid) polymer component having a water dispersability of at least about 5% by weight at 20° C. and an average molecular weight ranging from about 700 to about 4,000 daltons;   wherein the ratio of component (b) to component (a) is about 1:1 to about 1:10 by weight; and   (c) from about 20 to about 50% of a composition comprising either (i) a poly(lactide-co-glycolide) copolymer and a methyl poly(ethylene glycol) copolymer, or (ii) an acrylate/methacrylate-based polymer or copolymer and a methyl poly(ethylene glycol) copolymer;
           wherein the methyl poly(ethylene glycol) copolymer has a water solubility of at least about 5% by weight at 20° C., a hydrophilic-lipophilic balance value of at least about 7, and an average molecular weight ranging from 12,000 to 65,000, and further wherein the ratio of the poly(lactide-co-glycolide) or the acrylate/methacrylate-based polymer or copolymer, to the methyl poly(ethylene glycol) is about 1:1 to about 4:1 by weight and the ratio of component (c) to component (b) is about 2:1 to about 9:1 by weight.   
               

     Also disclosed is a geotropic propagule coated with the insecticidal composition. Further disclosed is a liquid composition comprising the insecticidal composition, and a method for protecting a geotropic propagule and plant derived therefrom from a phytophagous insect pest.

FIELD OF THE INVENTION

This invention relates to compositions comprising anthranilic diamideinsecticides and polymers in the combined form of nanoparticles. Thisinvention also relates to geotropic propagules coated with thesecompositions and to protecting propagules and derived plants fromphytophagous insect pests by contacting the propagules with thesecompositions.

BACKGROUND

Damage by phytophagous insect pests to geotropic propagules such asseeds, rhizomes, tubers, bulbs or corms, and plants derived therefromcauses significant economic losses.

Anthranilic diamides, alternatively called anthranilamides, are arecently discovered class of insecticides having activity againstnumerous insect pests of economic importance. PCT Publication WO03/024222 discloses treatment with anthranilic diamides being useful forprotecting propagules from phytophagous invertebrate pests. Furthermore,because of the ability of anthranilic diamides to translocate withinplants, not only the propagules, but also new growth developing from thepropagules can be protected.

Although anthranilic diamides have properties making them suitable forprotecting propagules and developing growth, achieving sufficientabsorption of anthranilic diamides into the propagule and developingroots to cause insecticidally effective concentrations in parts of thedeveloping plant for which protection is desired can be problematical.Although anthranilic diamide coatings on propagules are exposed tomoisture from the propagules and surrounding plant growing medium (e.g.,soil), the low water solubility of anthranilic diamide insecticidesimpedes their mobilization through moisture. Also, until the anthranilicdiamides are absorbed into the propagules and developing roots, they arevulnerable to absorption and dissipation through the growing medium.

Achieving insecticidally effective concentrations of anthranilicdiamides in foliage by treating propagules requires greater amounts ofanthranilic diamides to be available for transport greater distanceswithin the plant. Because the rapidly expanding volume of plant tissuein growing foliage inherently dilutes anthranilic diamideconcentrations, absorption of increased amounts of anthranilic diamidesis required for protection of foliage, particularly if protection offoliage beyond the first couple leaves and during a substantial part ofthe growing season is desired.

Accordingly, need exists for new compositions promoting the absorptionof anthranilic diamide insecticides into propagules and developingroots. Such compositions have now been discovered.

SUMMARY

One aspect of the present invention is an insecticidal compositioncomprising by weight based on the total weight of the composition:

-   -   (a) from about 0.25 to about 25% of one or more anthranilic        diamide insecticides;    -   (b) from about 2.5 to about 25% of a poly(lactic acid) polymer        component having a water dispersabilitiy of at least about 5% by        weight at 20° C. and an average molecular weight ranging from        about 700 to about 4,000 daltons;    -   wherein the ratio of component (b) to component (a) is about 1:1        to about 1:10 by weight; and    -   (c) from about 20 to about 50% of a composition comprising        either (i) a poly(lactide-co-glycolide) copolymer and a methyl        poly(ethylene glycol) copolymer, or (ii) an        acrylate/methacrylate-based polymer or copolymer and a methyl        poly(ethylene glycol) copolymer;        -   wherein the methyl poly(ethylene glycol) copolymer has a            water solubility of at least about 5% by weight at 20° C., a            hydrophilic-lipophilic balance value of at least about 7,            and an average molecular weight ranging from 12,000 to            65,000, and further wherein the ratio of the            poly(lactide-co-glycolide) or the            acrylate/methacrylate-based polymer or copolymer, to the            methyl poly(ethylene glycol) is about 1:1 to about 4:1 by            weight and the ratio of component (c) to component (b) is            about 2:1 to about 9:1 by weight.

Another aspect of the present invention is a geotropic propagule coatedwith an insecticidally effective amount of the aforedescribedcomposition.

Another aspect of the present invention is a liquid compositionconsisting of about 5 to 80 weight % of the aforedescribed compositionand about 20 to 95 weight % of an aqueous liquid carrier.

Another aspect of the present invention is a method for protecting ageotropic propagule and plant derived therefrom from a phytophagousinsect pest, the method comprising coating the propagule with aninsecticidally effective amount of the aforedescribed liquid compositionand then evaporating the aqueous liquid carrier of the composition.

DETAILED DESCRIPTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains,” “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process or method that comprises alist of elements is not necessarily limited to only those elements butmay include other elements not expressly listed or inherent to suchcomposition, mixture, process or method.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, or method that includes materials, steps, features,components, or elements, in addition to those literally disclosed,provided that these additional materials, steps, features, components,or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of.”

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), or both A and B are true (or present).

Similarly, when a range of values is cited, it should be presumed thatthe entire range includes the terminal values stated. In some cases, theterm “inclusive” serves to signal the inclusion of the terminal orflanking values in the disclosed range.

In the present disclosure and claims, the average molecular weight of acomponent is the number average molecular weight, which corresponds (fora given weight of the component) to multiplying the number of eachspecific subunit molecules of each molecular weight by that molecularweight, then adding the multiplication products, and finally dividingthe calculated sum by the total number of lactide and glycolide polymermolecules. Persons of ordinary skill in the art will readily appreciatethat specific techniques for determining molecular weight will provide avalue based on the number average molecular weight.

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e., occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in the present disclosure and claims, the term“propagule” means a seed or a regenerable plant part. The term“regenerable plant part” means a part of a plant other than a seed fromwhich a whole plant may be grown or regenerated when the plant part isplaced in horticultural or agricultural growing media such as moistenedsoil, peat moss, sand, vermiculite, perlite, rock wool, fiberglass,coconut husk fiber, tree fern fiber and the like, or even a completelyliquid medium such as water. The term “geotropic propagule” means a seedor a regenerable plant part obtained from the portion of a plantordinarily disposed below the surface of the growing medium. Geotropicregenerable plant parts include viable divisions of rhizomes, tubers,bulbs and corms which retain meristematic tissue, such as an eye.Regenerable plant parts such as cut or separated stems and leavesderived from the foliage of a plant are not geotropic and thus are notconsidered geotropic propagules. As referred to in the presentdisclosure and claims, unless otherwise indicated, the term “seed”specifically refers to unsprouted seeds. The term “foliage” refers toparts of a plant exposed above ground. Therefore foliage includesleaves, stems, branches, flowers, fruits and buds.

In the context of the present disclosure and claims, protection of aseed or plant grown therefrom from a phytophagous insect pest meansprotection of the seed or plant from injury or damage potentially causedby the insect pest. This protection is achieved through control of theinsect pest. Control of an insect pest can include killing the insectpest, interfering with its growth, development or reproduction, and/orinhibiting its feeding. In the present disclosure and claims the terms“insecticidal” and “insecticidally” relate to any form of insectcontrol.

The terms “suspension concentrate” and “suspension concentratecomposition” refer to compositions comprising finely divided solidparticles of an active ingredient dispersed in a continuous liquidphase. Said particles retain identity and can be physically separatedfrom the continuous liquid phase. The viscosity of the continuous liquidphase can vary from low to high, and indeed can be so high as to causethe suspension concentrate composition to have a gel-like or paste-likeconsistency.

The term “particle size” refers to the equivalent spherical diameter ofa particle, i.e., the diameter of a sphere enclosing the same volume asthe particle. “Median particle size” is the particle size correspondingto half of the particles being larger than the median particle size andhalf being smaller. With reference to particle size distribution,percentages of particles are also on a volume basis (e.g., “at least 95%of the particles are less than about 10 microns” means that at least 95%of the aggregate volume of particles consists of particles havingequivalent spherical diameters of less than about 10 microns). Theprinciples of particle size analysis are well-known to those skilled inthe art; for a technical paper providing a summary, see A. Rawle, “BasicPrinciples of Particle Size Analysis” (document MRK034 published byMalvern Instruments Ltd., Malvern, Worcestershire, UK). Volumedistributions of particles in powders can be conveniently measured bysuch techniques as Low Angle Laser Light Scattering (also known as LALLSand Laser Diffraction), which relies on the fact that diffraction angleis inversely proportional to particle size.

In the recitations herein, the term “alkyl” used either alone or incompound words such as “haloalkyl” or “fluoroalkyl” includesstraight-chain or branched alkyl, such as methyl, ethyl, n-propyl,i-propyl, or the different butyl isomers. “Alkoxy” includes, forexample, methoxy, ethoxy, n-propyloxy, isopropyloxy and the differentbutoxy isomers. The term “halogen,” either alone or in compound wordssuch as “haloalkyl,” includes fluorine, chlorine, bromine or iodine.Further, when used in compound words such as “haloalkyl” or“haloalkoxy,” said alkyl may be partially or fully substituted withhalogen atoms which may be the same or different. Examples of“haloalkyl” include CF₃, CH₂Cl, CH₂CF₃ and CCl₂CF₃. The terms“haloalkoxy,” and the like, are defined analogously to the term“haloalkyl.” Examples of “haloalkoxy” include OCF₃, OCH₂Cl₃, OCH₂CH₂CHF₂and OCH₂CF₃.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 4. Forexample, C₁-C₄ alkyl designates methyl through butyl, including thevarious isomers.

The present invention relates to the protection of a geotropic propaguleand plant derived therefrom from a phytophagous insect pest by coatingthe propagule with an insecticidally effective amount of an insecticidalcomposition comprising by weight based on the total weight of thecomposition:

-   -   (a) from about 0.25 to about 25% of one or more anthranilic        diamide insecticides;    -   (b) from about 2.5 to about 25% of a poly(lactic acid) polymer        component having a water dispersabilitiy of at least about 5% by        weight at 20° C. and an average molecular weight ranging from        about 700 to about 4,000 daltons;    -   wherein the ratio of component (b) to component (a) is about 1:1        to about 1:10 by weight; and    -   (c) from about 20 to about 50% of a composition comprising        either (i) a poly(lactide-co-glycolide) copolymer and a methyl        poly(ethylene glycol) copolymer, or (ii) an        acrylate/methacrylate-based polymer or copolymer and a methyl        poly(ethylene glycol) copolymer;        -   wherein the methyl poly(ethylene glycol) copolymer has a            water solubility of at least about 5% by weight at 20° C., a            hydrophilic-lipophilic balance value of at least about 7,            and an average molecular weight ranging from 12,000 to            65,000, and further wherein the ratio of the            poly(lactide-co-glycolide) or the            acrylate/methacrylate-based polymer or copolymer, to the            methyl poly(ethylene glycol) is about 1:1 to about 4:1 by            weight and the ratio of component (c) to component (b) is            about 2:1 to about 9:1 by weight.

In some embodiments, the inclusion in the composition of presentinvention of at least about 0.25% by weight and in a ratio of at leastabout 1:10 relative to component (a) and at least 2:1 of component (c)relative to component (b) of an anthranilic diamide insecticides andpolymers in the combined form of nanoparticles having the abovedescribed water solubility, HLB value, and average molecular weight hasbeen discovered to promote the absorption of the component (a) activeingredient into the propagule when the composition is coated on apropagule either directly or through the emerging roots, therebyproviding more uptake of anthranilic diamide insecticides into thedeveloping plant, including emerging foliage. Increasing uptake ofanthranilic diamide insecticides provides insecticidally effectiveconcentrations of the insecticides not only in the propagule, roots, andfoliage near ground level but also more distant foliage of the growingplant.

Anthranilic diamide insecticides, also known as anthranilamideinsecticides, are members of a class of insecticidal compoundscharacterized chemically by molecular structures comprising vicinalcarboxamide substituents bonded to the carbon atoms of an aryl ring,typically phenyl, wherein one carboxamide moiety is bonded through thecarbonyl carbon and the other carboxamide moiety is bonded through thenitrogen atom and characterized biologically by binding to ryanodinereceptors in insect muscle cells, causing the channel to open andrelease calcium ions into the cytoplasm. Depletion of calcium ion storesresults in insect paralysis and death. PCT Publication WO 2004/027042describes an assay for ryanodine receptor ligands. Illustrative ofanthranilic diamide insecticides are compounds of Formula 1, N-oxides,and salts thereof,

wherein

X is N, CF, CCl, CBr or Cl;

R¹ is CH₃, Cl, Br or F;

R² is H, F, Cl, Br or —CN;

R³ is F, Cl, Br, C₁-C₄ haloalkyl or C₁-C₄ haloalkoxy;

R^(4a) is H, C₁-C₄ alkyl, cyclopropylmethyl or 1-cyclopropylethyl;

R^(4b) is H or CH₃;

R⁵ is H, F, Cl or Br; and

R⁶ is H, F, Cl or Br.

A variety of anthranilic diamide insecticides and methods for theirpreparation are described in the literature. For example, compounds ofFormula 1 and methods for their preparation are reported in U.S. Pat.Nos. 6,747,047 and 7,247,647, and PCT Publications WO 2003/015518, WO2003/015519, WO 2004/067528, WO2006/062978 and WO2008/069990. It isnoteworthy that Yang and Sun (CN 101607940, 2009) disclosed preparationsof benzamide derivatives as insecticides useful for killing arthropodswherein X is C. Therefore, in addition to species wherein X=N, speciesof insecticides based on X=C, substituted or unsubstituted areencompassed by the invention disclosed herein.

Of particular note for the present compositions and methods of their useare compounds of Formula 1 wherein X is N; R¹ is CH₃; R² is Cl or —CN;R³ is Br; R^(4a) is CH₃; R^(4b) is H; R⁵ is Cl; and R⁶ is H. Thecompound wherein R² is C₁₋has the Chemical Abstracts systematic name3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamideand the common name chlorantraniliprole, and is trademarked as aninsecticidal active ingredient by DuPont as RYNAXYPYR. The compoundwherein R² is —CN has the Chemical Abstracts systematic name3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamideand the proposed common name cyantraniliprole, and is trademarked as aninsecticidal active ingredient by DuPont as CYAZYPYR. As disclosed inExample 15 of WO 2006/062978, cyantraniliprole is in the form of solidsmelting at 177-181° C. or 217-219° C. Both polymorphs are suitable forthe present compositions and methods.

Most generally, component (a) is from about 0.25 to about 25% of thecomposition by weight. Typically, component (a) is more typically atleast about 10%, and most typically at least 20% of the composition byweight. Component (a) is typically not more than about 23% and moretypically not more than about 21% of the composition by weight. Toprovide optimal biological availability, typically not more than about23% of component (a), more typically not more than about 21%, and mosttypically not more than about 20% of component (a) by weight is presentin the composition as particles having a particle size greater thanabout 100 nanometers. Particle sizes of 200 nanometers or less can beeasily achieved through preparation methods described herein.

The term “polylactic acid” refers to polymers of Formula 2

where each R₁ is independently selected from H and CH₃; andX is independently selected from integers from 5 to 50. The catalyststructure depicted in Formula 3, can be combined with monomers inFormula 4 to synthesize polymers of the type in Formula 2,

where M is independently selected from Zn and Mn and R₂ is independentlyselected from H or nothing and

where R₃ is independently selected from H and CH₃.

The polymerization is typically run in an air-free environment, and allreagents are treated to remove oxygen prior to use. The catalyst speciesis added to a reaction vessel, such that the ratio of catalyst speciesis less than 1:10, relative to the monomer species. The monomer is thenadded to the reaction vessel under nitrogen. Once the components aresolubilized in suitable organic solvent (THF) the reaction mixture ismaintained at the desired temperature. After the monomer is consumed,the reactions can be monitored using size-exclusion chromatography todetermine completion, which is signified by a molecular weight plateau.The solvent can be removed, e.g., under vacuum, to provide the desiredpolylactide.

The polylactide component (b) has an average molecular weight rangingfrom about 700 to about 4,000 daltons. In some embodiments, the averagemolecular weight of component (b) is at least about 200, 400, or 600daltons. In some embodiments, the average molecular weight of component(b) is not more than about 2,000 or 3,000 daltons.

In the present disclosure and claims, the average molecular weight ofthe polylactic acid polymer component is the number average, whichcorresponds (for a given weight of the component) to multiplying thenumber of polylactic acid polymer molecules of each molecular weight bytheir molecular weight, then adding the multiplication products, andfinally dividing the calculated sum by the total number of polylacticacid polymer molecules. However, other definitions of average molecularweight typically give values of a similar order of magnitude. Theaverage molecular weight of methyl methacrylate-based polymers can bemeasured by methods known in the art, such as gel permeationchromatography cited by Berger, Schulz, and Guenter Separation Science1971, 6(2), 297-303.

Typically, the molecules forming the polylactic acid polymer component(i.e., component (b)) do not all have the same molecular weight, butinstead molecular weights of the molecules form a distribution (e.g.,normal Gaussian). Generally, chemical synthesis processes to preparepolylactic acid polymer give unimodal distributions of molecularweights. Typically, at least about 90%, more typically at least about95% and most typically at least about 98%, of the polylactic acidpolymer molecules forming component (b) have molecular weights notexceeding about 10,000 daltons.

The structure depicted in Formula 2 could also be substituted with anumber of hydrophobic acrylate/methacrylate-based polymers in theabsence of using the catalyst from Formula 3 and the monomers fromFormula 4. The term “acrylate/methacrylate-based polymers” refers topolymers of Formula 5

where each R₄ is independently selected from H and CH₃; E isindependently selected from the initiating species of ethyl2-bromoisobutyrate, octadecyl 2-bromoisobutyrate, dodecyl2-bromoisobutyrate, 2-hydroxyethyl 2-bromoisobutyrate, and2,2,5-trimethyl-3-(1-phenylethoxy)-4-phenyl-3-azahexane, di-tert-butylperoxide, benzoyl peroxide, methyl ethyl ketone peroxide,Azobisisobutyronitrile 1,1′-Azobis(cyclohexanecarbonitrile); F isindependently selected from Cl, Br, or the transfer agentsdithiobenzoates, trithiocarbonates, dithiocarbamates, 2-cyano-2-propylbenzodithioate, 4-cyano-4-(phenylcarbonothioylthio)pentanoic acid,2-cyano-2-propyl dodecyltrithiocarbonate,4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, and2-(dodecylthiocarbonothioylthio)₂-methylpropionic acid; and Y areindependently selected from integers from 10 to 100.

As shown by the structure depicted in Formula 5, theacrylate/methacrylate-based polymers are substituted on the carboxylgroup with functional groups Q. Q can be benzyl, glycidyl, C₁-C₂₀straight chain alkyl, (e.g., methyl, ethyl, n-butyl, hexadecyl,octadecyl, lauryl, stearyl), C₃-C₂₀ branched alkyl (e.g., isodecyl,isooctyl, isotridecyl, tert-butyl), 2-phenoxyethyl, isobornyl ortetrahydro furfuryl, hydroxyethyl or 3-hydroxy propyl. Q can also be afunctional group derived from the reaction of a glycidyl group withcysteine, tryptophan, dihydroxyphenylalanine, phenylalanine, lysine,histidine, arginine, asparagine, glutamine, diethylene glycol,triethylene glycol, tetraethylene glycol, or 1,6-hexanediol. Thus,suitable Q groups include functional groups Q¹-Q¹⁶, shown below:

Methods for synthesizing acrylate/methacrylate-based copolymers arewell-known in the art. The acrylate/methacrylate copolymers disclosedherein can be synthesized by reacting two or more suitableacrylate/methacrylate monomers in the presence of an appropriatetransfer agent or metal catalyst system, and an appropriate initiatingspecies in a suitable solvent. The second monomer (Monomer 2) is addedafter the first monomer (Monomer 1) is fully polymerized (see e.g.,Table 2).

Suitable acrylate/methacrylate monomers are those which can formsecondary or tertiary radical active species and include one monomer ofFormula 6,

where R⁴ and Q are as defined above.

Suitable transfer agents include: dithiobenzoates, trithiocarbonates,dithiocarbamates, 2-cyano-2-propyl benzodithioate,4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, 2-cyano-2-propyldodecyltrithiocarbonate,4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, and2-(dodecylthiocarbonothioylthio)₂-methylpropionic acid.

Suitable metal catalyst systems include: copper (I) bromide/bipyridine;copper (I) bromide/4,4′-dinonyl-2,2′-dipyridyl; copper (I)bromide/N,N,N′,N″,N″-pentamethyldiethylenetriamine; copper (I)bromide/tris(2-pyridylmethyl)amine; copper (I)bromide/tris[2-(dimethylamino)ethyl]amine; copper (I)chloride/bipyridine; copper (I) chloride/4,4′-dinonyl-2,2′-dipyridyl;copper (I) chloride/N,N,N′,N″,N″-pentamethyldiethylenetriamine; copper(I) chloride/tris(2-pyridylmethyl)amine; and copper (I)chloride/tris[2-(dimethylamino)ethyl]amine.

Suitable initiating species include: ethyl 2-bromoisobutyrate, octadecyl2-bromoisobutyrate, dodecyl 2-bromoisobutyrate, 2-hydroxyethyl2-bromoisobutyrate, and2,2,5-trimethyl-3-(1-phenylethoxy)-4-phenyl-3-azahexane.

Suitable solvents include: tetrahydrofuran, acetone, and ethanol.

The polymerization is typically run in an air-free environment, and allreagents are treated to remove oxygen prior to use. A transfer agent orcatalyst species and the initiator species are typically added to areaction vessel, such that the ratio of transfer agent (or catalystspecies) is less than 1:1, relative to the initiator species. Themonomer is then added to the reaction vessel under nitrogen. Once thecomponents are solubilized, the initiating species is added and thereaction mixture is maintained at the desired temperature. After themonomer is consumed reactions can be monitored using size-exclusionchromatography to determine completion, which is signified by amolecular weight plateau. Residual transfer agents and/or catalystspecies can be removed by conventional means, such as columnchromatography. The solvent can be removed, e.g., under vacuum, toprovide the desired polymer.

The acrylate/methacrylate-based polymer component (b) has an averagemolecular weight ranging from about 1,000 to about 20,000 daltons. Insome embodiments, the average molecular weight of component (b) is atleast about 500, 700, or 900 daltons. In some embodiments, the averagemolecular weight of component (b) is not more than about 10,000 or15,000 daltons.

In the present disclosure and claims, the average molecular weight ofthe acrylate/methacrylate-based polymer component is the number average,which corresponds (for a given weight of the component) to multiplyingthe number of acrylate/methacrylate-based polymer molecules of eachmolecular weight by their molecular weight, then adding themultiplication products, and finally dividing the calculated sum by thetotal number of acrylate/methacrylate-based polymer molecules. However,other definitions of average molecular weight typically give values of asimilar order of magnitude. The average molecular weight of methylmethacrylate-based polymers can be measured by methods known in the art,such as gel permeation chromatography cited by Berger, Schulz, andGuenter Separation Science 1971, 6(2), 297-303. Manufacturers of methoxyethylene glycol methacrylate monomers that can be used to synthesize theacrylate/methacrylate-based polymers of this invention generallydisclose average molecular weight information, and this information canbe used to select acrylate/methacrylate-based polymers for component (b)of the present composition.

Typically, the molecules forming the acrylate/methacrylate-based polymercomponent (i.e., component (b)) do not all have the same molecularweight, but instead molecular weights of the molecules form adistribution (e.g., normal Gaussian). Generally, chemical synthesisprocesses to prepare acrylate/methacrylate-based polymers give unimodaldistributions of molecular weights. However, component (b) of thepresent composition can comprise acrylate/methacrylate-based polymersprepared with polyethylene oxide units of different lengths in apolydisperse form. Therefore, the molecular weight distribution of themethoxy ethylene glycol component of (b) can be bimodal or evenmultimodal. Typically, at least about 90%, more typically at least about95% and most typically at least about 98%, of theacrylate/methacrylate-based polymer molecules forming component (b) havemolecular weights not exceeding about 20,000 daltons.

Acrylate/methacrylate-based polymers typically have units functionalizedwith Q groups, with an average molecular weight of at least about 2,000daltons, which corresponds to the average value for the subscriptvariable “Y” in Formula 5 being at least about 20. More typically, theaverage molecular weight of the blocks of acrylate/methacrylate-basedunits containing Q groups is greater than 3,000 daltons. Typically,10≦Y≦100.

In the present composition, component (b) (i.e., theacrylate/methacrylate-based polymer or polylactic acid component) has awater dispersibility of at least about 5% by weight at 20° C.Accordingly, component (b) is dispersible in water at 20° C. to theextent of at least about 5% (by weight), which means that a saturatedsolution or liquid crystalline phase of component (b) in water at 20° C.contains at least about 5% by weight of component (b). (For simplicity,water solubility is accordingly defined in the present disclosure aspercent by weight even if “by weight” is not expressly stated.) Ifcomponent (b) contains multiple acrylate/methacrylate-based polymer orpolylactic acid constituents, typically each constituent has a waterdispersibility of at least about 5% at 20° C. Mostacrylate/methacrylate-based polymers or polylactic acids suitable forcomponent (b) have significantly greater water dispersibilities (e.g.,greater than 10%) and many are miscible with water (e.g., soluble inwater in all proportions). Decreased absorption of anthranilic diamideinsecticides into a propagule and/or developing roots is observed whenwater-insoluble acrylate/methacrylate-based polymers are substituted foracrylate/methacrylate-based polymers having water dispersibility of atleast about 5% as component (b) in a composition coating a seed in soil.

The term poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) refers tothe polymer structures in Formula 7 below, which can be combined with apolymer of the form of either Formula 2 or Formula 5,

where m varies independently from 2 to 200 and suitable Z groups fromZ¹-Z² are shown below:

where k varies independently from 2 to 200.

The polymerization of poly(lactide-co-glycolide)/methylatedpoly(ethylene glycol) (PLGA-mPEG) is typically run in an airenvironment. A pre-synthesized polymer of methylated poly(ethyleneglycol) is added to a test tube. The monomers from Formula 4 can beadded at an appropriate ratio to designate the intended biodegradationbehavior for future application followed by a tin octoate catalyst andthe flask is sealed and placed in a vacuum oven set to 140° C.overnight. After the monomer is consumed reactions can be monitoredusing size-exclusion chromatography to determine completion, which issignified by a molecular weight plateau. Residual catalyst species canbe removed by conventional means, such as column chromatography.

The PLGA component (b) has an average molecular weight ranging fromabout 12,000 to about 65,000 daltons. In some embodiments, the averagemolecular weight of component (b) is at least about 15,000, 20,000, or25,000 daltons. In some embodiments, the average molecular weight ofcomponent (b) is not more than about 50,000 or 60,000 daltons. The finalratio of PLGA component to mPEG component can be as high as 1 to 1 andas low as 4 to 1.

In the present disclosure and claims, the average molecular weight ofthe PLGA component is the number average, which corresponds (for a givenweight of the component) to multiplying the number of lactide andglycolide polymer molecules of each molecular weight by their molecularweight, then adding the multiplication products, and finally dividingthe calculated sum by the total number of lactide and glycolide polymermolecules.

The polymerization of the acrylate/methacrylate-based polymer componentis typically run in an air-free environment, and all reagents aretreated to remove oxygen prior to use. A transfer agent or catalystspecies and the initiator species are typically added to a reactionvessel, such that the ratio of transfer agent (or catalyst species) isless than 1:1, relative to the initiator species. The monomer is thenadded to the reaction vessel under nitrogen. Once the components aresolubilized, the initiating species is added and the reaction mixture ismaintained at the desired temperature. After the monomer is consumedreactions can be monitored using size-exclusion chromatography todetermine completion, which is signified by a molecular weight plateau.Residual transfer agents and/or catalyst species can be removed byconventional means, such as column chromatography. The solvent can beremoved, e.g., under vacuum, to provide the desired polymer.

The acrylate/methacrylate-based polymer component (b) has an averagemolecular weight ranging from about 12,000 to about 65,000 daltons. Insome embodiments, the average molecular weight of component (b) is atleast about 15,000, 20,000, or 25,000 daltons. In some embodiments, theaverage molecular weight of component (b) is not more than about 50,000or 60,000 daltons. The final ratio of acrylate/methacrylate-basedcomponent to mPEG component can be as high as 1 to 1 and as low as 4 to1.

In the present disclosure and claims, the average molecular weight ofthe acrylate/methacrylate-based polymer component is the number average,which corresponds (for a given weight of the component) to multiplyingthe number of acrylate/methacrylate-based polymer molecules of eachmolecular weight by their molecular weight, then adding themultiplication products, and finally dividing the calculated sum by thetotal number of acrylate/methacrylate-based polymer molecules.

Suitable transfer agents include: dithiobenzoates, trithiocarbonates,dithiocarbamates, 2-cyano-2-propyl benzodithioate,4-cyano-4-(phenylcarbonothioylthio)pentanoic acid, 2-cyano-2-propyldodecyltrithiocarbonate,4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, and2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid.

Suitable metal catalyst systems include: copper (I) bromide/bipyridine;copper (I) bromide/4,4′-dinonyl-2,2′-dipyridyl; copper (I)bromide/N,N,N′,N″,N″-pentamethyldiethylenetriamine; copper (I)bromide/tris(2-pyridylmethyl)amine; copper (I)bromide/tris[2-(dimethylamino)ethyl]amine; copper (I)chloride/bipyridine; copper (I) chloride/4,4′-dinonyl-2,2′-dipyridyl;copper (I) chloride/N,N,N′,N″,N-pentamethyldiethylenetriamine; copper(I) chloride/tris(2-pyridylmethyl)amine; and copper (I)chloride/tris[2-(dimethylamino)ethyl]amine.

Suitable initiating species include: methyl(PEG) 2-bromoisobutyrate.

Suitable solvents include: tetrahydrofuran, acetone, and ethanol.

To prepare nanoparticles comprised of polymer/anthranilic diamidecompositions, polymers from Formula 2 or Formula 5 can be added to anaqueous solution of polymers from Formula 7 under specific ratios. Theaqueous solution can be as low as 1% PLGA or acrylate/methacrylate-basedpolymer/mPEG and as high as 25% PLGA or acrylate/methacrylate-basedpolymer/mPEG. The ratio of PLGA or acrylate/methacrylate-basedpolymer/mPEG to PLA can be as low as 2 to 1 and as high as 9 to 1 toachieve nanoparticles. Nanoparticles as it is referred to in the presentdocument signifies particles less than or equal to 150 nm using dynamiclight scattering or particle size analysis with the particle sizedocumented being in the d50 range. Upon combination of ingredients thesolutions are stirred for 4 hours after which the particle size isconfirmed by particle analysis, scanning electron microscopy, andtransmission electron microscopy.

The hydrophilic-lipophilic balance (HLB) of a surfactant is an overallmeasure of the degree to which it is hydrophilic or lipophilic, and isdetermined by the ratio of polar and non-polar groups in the surfactantmolecule. The HLB number of a surfactant indicates the polarity of thesurfactant molecules in an arbitrary range of 1 to 40, wherein thenumber increases with increasing hydrophilicity. The HLB number for asurfactant can be determined by the “emulsion comparison method” ofGriffin (W. C. Griffin, J. Soc. Cosmet. Chem. 1949, 1, 311-326).

The poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymercomponent (i.e., component (c)) of the present composition has an HLBvalue of at least about 3. Poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymercomponents having HLB values less than about 3 typically have limitedwater solubility, which can be less than 5% at 20° C.Poly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymers having HLB values near 1 are generallyregarded as insoluble in water. Although poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymercomponents having HLB values less than about 3 in combination withcomponent (b) can promote absorption of the component (a) activeingredient into propagules and developing roots, their ability topromote the desired absorption in a soil medium is observed to besignificantly less than for components having HLB values of at leastabout 3. Typically, the HLB value of component (c) is greater than 5,such as 6, 7 or 8. In certain embodiments, the HLB value of component(c) is at least about 10. Embodiments wherein the HLB value of component(c) is at least about 20 are of particular note, becauseacrylate/methacrylate-based polymers having HLB values at least about 20are typically very water soluble (i.e., >25% water solubility at 20°C.). High water solubility facilitates preparing highly concentratedliquid compositions from moderate amounts of water, which reduces theamount of water that needs to be evaporated after coating propagules.Although component (c) having a high HLB value is particularly useful inthe present composition, the HLB range is limited to 40. Usuallycomponent (c) has a HLB value of not more than about 35. Typically,commercially available poly(lactide-co-glycolide) or(acrylate/methacrylate-based)/methylated poly(ethylene glycol) triblockcopolymers do not have an HLB value of more than about 31. Component (c)can have an HLB value of not more than about 20 or not more than about15.

The HLB value desired for the poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymercomponent can be achieved by mixing in the proper ratio two or morepoly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymers having HLB values above and below thedesired HLB value. The HLB value for a combination of surfactants isgenerally close to the value calculated based on HLB contributions ofthe constituent surfactants according to their weight percentages.Component (c) can contain an poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymerhaving an HLB value of less than 3 if component (c) also contains asufficient amount of one or more other poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymershaving HLB values greater than 5, so that the resulting HLB value ofcomponent (c) is at least about 3. For example, a mixture of twopoly(lactide-co-glycolide) (or acrylate/methacrylate-based)methylatedpoly(ethylene glycol) copolymers having HLB values of 1 and 15 in a 1:8ratio by weight has an HLB value greater than 5. Typically, the HLBvalue of each constituent in a mixture of poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersforming component (c) is at least about 3.

For poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersused in component (c), the total molecular weight of the pendant group(i.e., Q group) is typically in the range of about 20% to about 90% ofthe weight of the molecule. A pendant group with hydrophilic content ofat least about 20% provides water solubility of at least about 5% at 20°C. A pendant group with hydrophilic content of at least about 60%typically provides high water solubility (i.e., >25% water solubility at20° C.), which facilitates preparing concentrated aqueous liquidcompositions. Although the hydrophilic content can be 90% or evenhigher, more typically the total molecular weight of the hydrophilicpendant group is not more than about 80% of the weight of the molecule.

The physical consistency of poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersin their pure form ranges from liquids to viscous solids to solids(typically described as waxes) at 20° C. Poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymershaving an HLB value of at least about 18 are typically solids at 20° C.,while poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymershaving lower HLB values are typically liquids or viscous solidsdepending upon both HLB value and molecular weight (lower HLB and lowermolecular weight favoring liquids versus viscous solids).Poly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymers that are viscous solids or solidsfacilitate component (c) functioning as an adhesive to affix thecomposition to a hydrophobic polymer (i.e. polylactic acid) orpropagule. Poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersthat are solids are of particular note as constituents of component (c),because they provide durable coatings without needing to includeadditional adhesives such as film formers in the composition.

The inclusion of hydrophobic groups (e.g., Q groups as described above)in combination with mPEG provides poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymermolecules with an amphiphilic combination of well-defined hydrophilicand lipophilic regions, thereby resulting in the ability to function asa surfactant.

Generally, increasing the weight ratio of components (b) and (c) tocomponent (a) increases the absorption of component (a) into thepropagule and/or developing roots to protect also the foliage of a plantgrown from a propagule coated with a composition comprising components(a), (b), and (c). However, increasing components (b) and (c) alsoreduces the amount of component (a) that can be included in thecomposition. Generally, the weight ratio of component (b) and (c) tocomponent (a) is at least about 1:1000, typically at least about 1:900,more typically from at least about 1:700 or 1:500, and most typically atleast about 1:300. In some embodiments the weight ratio of component (a)to component (b) and (c) is at least about 1:100 or 1:30. Generally, theweight ratio of components (b) and (c) to component (a) is not more thanabout 1000:1, typically not more than about 900:1, more typically notmore than about 700:1, and most typically not more than about 300:1. Insome embodiments the weight ratio of component (a) to components (b) and(c) is not more than about 100:1 or 30:1.

Most generally, components (b) and (c) are from about 9 to about 91% ofthe composition by weight. Increasing the amount of components (b) and(c) can increase the ratio of components (b) and (c) to component (a) tofacilitate absorption of component (a) from the propagule coating intothe propagule and/or developing roots, but also reduces theconcentration of component (a) in the coating and accordingly requires athicker coating to provide a desired amount of component (a) for eachpropagule. Typically, components (b) and (c) are at least about 15%,more typically at least about 20%, and most typically at least 25% ofthe composition by weight. In some embodiments, components (b) and (c)are at least about 30%, 35% or 40% of the composition by weight.Components (b) and (c) are typically not more than about 80%, moretypically not more than about 70%, and most typically not more thanabout 60% of the composition by weight. In some embodiments, component(b) and (c) is not more than about 50% or 40% of the composition byweight.

The present composition can optionally further comprise (d) up to about90% by weight of one or more biologically active agents other thananthranilic diamide insecticides. Biologically active agents ofcomponent (d) do not include biocides whose principal effect is topreserve the present composition rather than protect a plant contactedwith the present composition.

If present, component (d) is typically at least about 0.1% and moretypically at least about 1% of the composition by weight. Typically,component (d) is not more than about 60%, more typically not more thanabout 50%, 40% or 30%, and most typically not more than about 20% of thecomposition by weight. The biologically active agents forming component(d) differ from the component (a) anthranilic diamide insecticides andcan include chemical compounds or biological organisms selected from thefollowing classes: insecticides, fungicides, nematocides, bactericides,acaricides, herbicides, growth regulators such as rooting stimulants,chemosterilants, semiochemicals, repellents, attractants, pheromones andfeeding stimulants (including both chemical and biological agents), andmixtures of several compounds or organisms selected from the aboveclasses.

Compositions comprising different biologically active agents can have abroader spectrum of activity than a single agent alone. Furthermore,such mixtures can exhibit a synergistic effect.

Examples of component (d) (i.e., the one or more biologically activeagents other than anthranilic diamide insecticides) include:insecticides such as abamectin, acephate, acequinocyl, acetamiprid,acrinathrin, amidoflumet, amitraz, avermectin, azadirachtin,azinphos-methyl, bifenthrin, bifenazate, bistrifluoron, borate,buprofezin, cadusafos, carbaryl, carbofuran, cartap, carzol,chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos,chlorpyrifos-methyl, chromafenozide, clofentezin, clothianidin,cyantraniliprole, cyflumetofen, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin,dimehypo, dimethoate, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide,fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil,flonicamid, flubendiamide, flucythrinate, flufenerim, flufenoxuron,fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate,halofenozide, hexaflumuron, hexythiazox, hydramethylnon, imidacloprid,indoxacarb, insecticidal soaps, isofenphos, lufenuron, malathion,metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb,methomyl, methoprene, methoxychlor, metofluthrin, monocrotophos,methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron,oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone,phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite,protrifenbute, pymetrozine, pyrafluprole, pyrethrin, pyridaben,pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, rotenone,ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen,spirotetramat, sulprofos, tebufenozide, tebufenpyrad, teflubenzuron,tefluthrin, terbufos, tetrachlorvinphos, tetramethrin, thiacioprid,thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin,triazamate, trichlorfon, triflumuron, Bacillus thuringiensisdelta-endotoxins, entomopathogenic bacteria, entomopathogenic virusesand entomopathogenic fungi.

Of note are insecticides such as abamectin, acetamiprid, acrinathrin,amitraz, avermectin, azadirachtin, bifenthrin, buprofezin, cadusafos,carbaryl, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos,clothianidin, cyantraniliprole, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, flufenoxuron, fluvalinate,formetanate, fosthiazate, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, metaflumizone, methiodicarb, methomyl,methoprene, methoxyfenozide, nitenpyram, nithiazine, novaluron, oxamyl,pymetrozine, pyrethrin, pyridaben, pyridalyl, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,tebufenozide, tetramethrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumuron, Bacillusthuringiensis delta-endotoxins, all strains of Bacillus thuringiensisand all strains of Nucleo polyhydrosis viruses.

One embodiment of biological agents for mixing with compounds of thisinvention include entomopathogenic bacteria such as Bacillusthuringiensis, and the encapsulated delta-endotoxins of Bacillusthuringiensis such as MVP® and MVPII® bioinsecticides prepared by theCellCap® process (CellCap®, MVP® and MVPII® are trademarks of MycogenCorporation, Indianapolis, Ind., USA); entomopathogenic fungi such asgreen muscardine fungus; and entomopathogenic (both naturally occurringand genetically modified) viruses including baculovirus, nucleopolyhedrovirus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV),Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus(GV) such as Cydia pomonella granulosis virus (CpGV).

Of particular note is such a combination where the other biologicallyactive agent belongs to a different chemical class or has a differentsite of action than the compound of Formula 1. In certain instances, acombination with at least one other biologically active agent having asimilar spectrum of control but a different site of action will beparticularly advantageous for resistance management. Thus, a compositionof the present invention can further comprise at least one additionalbiologically active agent having a similar spectrum of control butbelonging to a different chemical class or having a different site ofaction. These additional biologically active compounds or agentsinclude, but are not limited to, sodium channel modulators such asbifenthrin, cypermethrin, cyhalothrin, lambda-cyhalothrin, cyfluthrin,beta-cyfluthrin, deltamethrin, dimefluthrin, esfenvalerate, fenvalerate,indoxacarb, metofluthrin, profluthrin, pyrethrin and tralomethrin;cholinesterase inhibitors such as chlorpyrifos, methomyl, oxamyl,thiodicarb and triazamate; neonicotinoids such as acetamiprid,clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine,thiacioprid and thiamethoxam; insecticidal macrocyclic lactones such asspinetoram, spinosad, abamectin, avermectin and emamectin; GABA(□□aminobutyric acid)-gated chloride channel antagonists such asavermectin or blockers such as ethiprole and fipronil; chitin synthesisinhibitors such as buprofezin, cyromazine, flufenoxuron, hexaflumuron,lufenuron, novaluron, noviflumuron and triflumuron; juvenile hormonemimics such as diofenolan, fenoxycarb, methoprene and pyriproxyfen;octopamine receptor ligands such as amitraz; molting inhibitors andecdysone agonists such as azadirachtin, methoxyfenozide andtebufenozide; ryanodine receptor ligands such as ryanodine, anthranilicdiamides such as chlorantraniliprole, cyantraniliprole andflubendiamide; nereistoxin analogs such as cartap; mitochondrialelectron transport inhibitors such as chlorfenapyr, hydramethylnon andpyridaben; lipid biosynthesis inhibitors such as spirodiclofen andspiromesifen; cyclodiene insecticides such as dieldrin or endosulfan;pyrethroids; carbamates; insecticidal ureas; and biological agentsincluding nucleopolyhedro viruses (NPV), members of Bacillusthuringiensis, encapsulated delta-endotoxins of Bacillus thuringiensis,and other naturally occurring or genetically modified insecticidalviruses.

Further examples of biologically active compounds or agents with whichcompounds of this invention can be formulated are: fungicides such asacibenzolar, aldimorph, amisulbrom, azaconazole, azoxystrobin,benalaxyl, benomyl, benthiavalicarb, benthiavalicarb-isopropyl,binomial, biphenyl, bitertanol, blasticidin-S. Bordeaux mixture(Tribasic copper sulfate), boscalid/nicobifen, bromuconazole,bupirimate, buthiobate, carboxin, carpropamid, captafol, captan,carbendazim, chloroneb, chlorothalonil, chlozolinate, clotrimazole,copper oxychloride, copper salts such as copper sulfate and copperhydroxide, cyazofamid, cyflunamid, cymoxanil, cyproconazole, cyprodinil,dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb,difenoconazole, dimethomorph, dimoxystrobin, diniconazole,diniconazole-M, dinocap, discostrobin, dithianon, dodemorph, dodine,econazole, etaconazole, edifenphos, epoxiconazole, ethaboxam, ethirimol,ethridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole,fencaramid, fenfuram, fenhexamide, fenoxanil, fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferfurazoate,ferimzone, fluazinam, fludioxonil, flumetover, fluopicolide,fluoxastrobin, fluquinconazole, fluquinconazole, flusilazole,flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum,fuberidazole, furalaxyl, furametapyr, hexaconazole, hymexazole,guazatine, imazalil, imibenconazole, iminoctadine, iodicarb, ipconazole,iprobenfos, iprodione, iprovalicarb, isoconazole, isoprothiolane,kasugamycin, kresoxim-methyl, mancozeb, mandipropamid, maneb,mapanipyrin, mefenoxam, mepronil, metalaxyl, metconazole,methasulfocarb, metiram, metominostrobin/fenominostrobin, mepanipyrim,metrafenone, miconazole, myclobutanil, neo-asozin (ferricmethanearsonate), nuarimol, octhilinone, ofurace, orysastrobin,oxadixyl, oxolinic acid, oxpoconazole, oxycarboxin, paclobutrazol,penconazole, pencycuron, penthiopyrad, perfurazoate, phosphonic acid,phthalide, picobenzamid, picoxystrobin, polyoxin, probenazole,prochloraz, procymidone, propamocarb, propamocarb-hydrochloride,propiconazole, propineb, proquinazid, prothioconazole, pyraclostrobin,pryazophos, pyrifenox, pyrimethanil, pyrifenox, pyroInitrine,pyroquilon, quinconazole, quinoxyfen, quintozene, silthiofam,simeconazole, spiroxamine, streptomycin, sulfur, tebuconazole,techrazene, tedoftalam, tecnazene, tetraconazole, thiabendazole,thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil,tolclofos-methyl, tolyfluanid, triadimefon, triadimenol, triarimol,triazoxide, tridemorph, trimoprhamide tricyclazole, trifloxystrobin,triforine, triticonazole, uniconazole, validamycin, vinclozolin, zineb,ziram, and zoxamide; nematocides such as aldicarb, imicyafos, oxamyl andfenamiphos; bactericides such as streptomycin; acaricides such asamitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol,dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin,fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.

In certain instances, combinations of a compound of this invention withother biologically active (particularly invertebrate pest control)compounds or agents (i.e. active ingredients) can result in agreater-than-additive (i.e., synergistic) effect. Reducing the quantityof active ingredients released in the environment while ensuringeffective pest control is always desirable. When synergism withbiologically active agents occurs at application rates givingagronomically satisfactory levels of insect control, such combinationscan be advantageous for reducing crop production cost and decreasingenvironmental load.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to insect pests(such as Bacillus thuringiensis delta-endotoxins). Such an applicationmay provide a broader spectrum of plant protection and be advantageousfor resistance management. The effect of the exogenously appliedcompounds of this invention may be synergistic with the expressed toxinproteins.

General references for these agricultural protectants (i.e.,insecticides, fungicides, nematocides, acaricides, herbicides andbiological agents) include The Pesticide Manual, 13th Edition, C. D. S.Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K.,2003 and The BioPesticide Manual, 2^(nd) Edition, L. G. Copping, Ed.,British Crop Protection Council, Famham, Surrey, U.K., 2001.

Table A lists specific combinations of a compound of Formula 1 withother biologically active agents illustrative of the mixtures,compositions and methods of the present invention and includesadditional embodiments of weight ratio ranges for application rates. Thefirst column of Table A lists the specific insect control agents (e.g.,“Abamectin” in the first line). The second column of Table A lists themode of action (if known) or chemical class of the insect pest controlagents. The third column of Table A lists embodiment(s) of ranges ofweight ratios for rates at which the insect pest control agent can beapplied relative to a compound of Formula 1 (e.g., “50:1 to 1:50” ofabamectin relative to a compound of Formula 1 by weight). Thus, forexample, the first line of Table A specifically discloses thecombination of a compound of Formula 1 with abamectin can be applied ina weight ratio between 50:1 to 1:50. The remaining lines of Table A areto be construed similarly.

TABLE A Invertebrate Pest Mode of Action or Typical Control AgentChemical Class Weight Ratio Abamectin macrocyclic lactones 50:1 to 1:50Acetamiprid neonicotinoids 150:1 to 1:200 Amitraz octopamine receptorligands 200:1 to 1:100 Avermectin macrocyclic lactones 50:1 to 1:50Azadirachtin ecdysone agonists 100:1 to 1:120 Beta-cyfluthrin sodiumchannel modulators 150:1 to 1:200 Bifenthrin sodium channel modulators100:1 to 1:10 Buprofezin chitin synthesis inhibitors 500:1 to 1:50Cartap nereistoxin analogs 100:1 to 1:200 Chlorantraniliprole ryanodinereceptor ligands 100:1 to 1:120 Chlorfenapyr mitochondrial electron300:1 to 1:200 transport inhibitors Chlorpyrifos cholinesteraseinhibitors 500:1 to 1:200 Clothianidin neonicotinoids 100:1 to 1:400Cyantraniliprole ryanodine receptor ligands 100:1 to 1:120 Cyfluthrinsodium channel modulators 150:1 to 1:200 Cyhalothrin sodium channelmodulators 150:1 to 1:200 Cypermethrin sodium channel modulators 150:1to 1:200 Cyromazine chitin synthesis inhibitors 400:1 to 1:50Deltamethrin sodium channel modulators 50:1 to 1:400 Dieldrin cyclodieneinsecticides 200:1 to 1:100 Dinotefuran neonicotinoids 150:1 to 1:200Diofenolan molting inhibitor 150:1 to 1:200 Emamectin macrocycliclactones 50:1 to 1:10 Endosulfan cyclodiene insecticides 200:1 to 1:100Esfenvalerate sodium channel modulators 100:1 to 1:400 EthiproleGABA-regulated chloride 200:1 to 1:100 channel blockers Fenothiocarb150:1 to 1:200 Fenoxycarb juvenile hormone mimics 500:1 to 1:100Fenvalerate sodium channel modulators 150:1 to 1:200 FipronilGABA-regulated chloride 150:1 to 1:100 channel blockers Flonicamid 200:1to 1:100 Flubendiamide ryanodine receptor ligands 100:1 to 1:120Flufenoxuron chitin synthesis inhibitors 200:1 to 1:100 Hexaflumuronchitin synthesis inhibitors 300:1 to 1:50 Hydramethylnon mitochondrialelectron 150:1 to 1:250 transport inhibitors Imidacloprid neonicotinoids1000:1 to 1:1000 Indoxacarb sodium channel modulators 200:1 to 1:50Lambda-cyhalothrin sodium channel modulators 50:1 to 1:250 Lufenuronchitin synthesis inhibitors 500:1 to 1:250 Metaflumizone 200:1 to 1:200Methomyl cholinesterase inhibitors 500:1 to 1:100 Methoprene juvenilehormone mimics 500:1 to 1:100 Methoxyfenozide ecdysone agonists 50:1 to1:50 Nitenpyram neonicotinoids 150:1 to 1:200 Nithiazine neonicotinoids150:1 to 1:200 Novaluron chitin synthesis inhibitors 500:1 to 1:150Oxamyl cholinesterase inhibitors 200:1 to 1:200 Pymetrozine 200:1 to1:100 Pyrethrin sodium channel modulators 100:1 to 1:10 Pyridabenmitochondrial electron 200:1 to 1:100 transport inhibitors Pyridalyl200:1 to 1:100 Pyriproxyfen juvenile hormone mimics 500:1 to 1:100Ryanodine ryanodine receptor ligands 100:1 to 1:120 Spinetorammacrocyclic lactones 150:1 to 1:100 Spinosad macrocyclic lactones 500:1to 1:10 Spirodiclofen lipid biosynthesis inhibitors 200:1 to 1:200Spiromesifen lipid biosynthesis inhibitors 200:1 to 1:200 Tebufenozideecdysone agonists 500:1 to 1:250 Thiacloprid neonicotinoids 100:1 to1:200 Thiamethoxam neonicotinoids 1250:1 to 1:1000 Thiodicarbcholinesterase inhibitors 500:1 to 1:400 Thiosultap-sodium 150:1 to1:100 Tralomethrin sodium channel modulators 150:1 to 1:200 Triazamatecholinesterase inhibitors 250:1 to 1:100 Triflumuron chitin synthesisinhibitors 200:1 to 1:100 Bacillus thuringiensis biological agents 50:1to 1:10 Bacillus thuringiensis biological agents 50:1 to 1:10delta-endotoxin NPV (e.g., Gemstar) biological agents 50:1 to 1:10

Of note is the composition of the present invention wherein the at leastone additional biologically active compound or agent is selected fromthe insect pest control agents listed in Table A above.

The weight ratios of a compound of Formula 1, an N-oxide, or a saltthereof, to the additional insect pest control agent typically arebetween 1,000:1 and 1:1,000, with one embodiment being between 500:1 and1:500, another embodiment being between 250:1 and 1:200 and anotherembodiment being between 100:1 and 1:50.

Listed below in Tables B1 and B2 are embodiments of specificcompositions comprising a compound of Formula 1 (Compound 1 is3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamideand Compound 2 is3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide)and an additional insect pest control agent.

TABLE B1 Mixture Cmpd. Invertebrate Pest No. No. and Control Agent B1-11 and Abamectin B1-2 1 and Acetamiprid B1-3 1 and Amitraz B1-4 1 andAvermectin B1-5 1 and Azadirachtin B1-5a 1 and Bensultap B1-6 1 andBeta-cyfluthrin B1-7 1 and Bifenthrin B1-8 1 and Buprofezin B1-9 1 andCartap B1-10 1 and Chlorantraniliprole B1-11 1 and Chlorfenapyr B1-12 1and Chlorpyrifos B1-13 1 and Clothianidin B1-14 1 and CyantraniliproleB1-15 1 and Cyfluthrin B1-16 1 and Cyhalothrin B1-17 1 and CypermethrinB1-18 1 and Cyromazine B1-19 1 and Deltamethrin B1-20 1 and DieldrinB1-21 1 and Dinotefuran B1-22 1 and Diofenolan B1-23 1 and EmamectinB1-24 1 and Endosulfan B1-25 1 and Esfenvalerate B1-26 1 and EthiproleB1-27 1 and Fenothiocarb B1-28 1 and Fenoxycarb B1-29 1 and FenvalerateB1-30 1 and Fipronil B1-31 1 and Flonicamid B1-32 1 and FlubendiamideB1-33 11  and Flufenoxuron B1-34 1 and Hexaflumuron B1-35 1 andHydramethylnon B1-36 1 and Imidacloprid B1-37 1 and Indoxacarb B1-38 1and Lambda-cyhalothrin B1-39 1 and Lufenuron B1-40 1 and MetaflumizoneB1-41 1 and Methomyl B1-42 1 and Methoprene B1-43 1 and MethoxyfenozideB1-44 1 and Nitenpyram B1-45 1 and Nithiazine B1-46 1 and NovaluronB1-47 1 and Oxamyl B1-48 1 and Phosmet B1-49 1 and Pymetrozine B1-50 1and Pyrethrin B1-51 1 and Pyridaben B1-52 1 and Pyridalyl B1-53 1 andPyriproxyfen B1-54 1 and Ryanodine B1-55 1 and Spinetoram B1-56 1 andSpinosad B1-57 1 and Spirodiclofen B1-58 1 and Spiromesifen B1-59 1 andSpirotetramat B1-60 1 and Tebufenozide B1-61 1 and Thiacloprid B1-62 1and Thiamethoxam B1-63 1 and Thiodicarb B1-64 1 and Thiosultap-sodiumB1-65 1 and Tolfenpyrad B1-66 1 and Tralomethrin B1-67 1 and TriazamateB1-68 1 and Triflumuron B1-69 1 and Bacillus thuringiensis B1-70 1 andBacillus thuringiensis delta-endotoxin B1-71 1 and NPV (e.g., Gemstar)

TABLE B2 Mixture Cmpd. Invertebrate Pest No. No. and Control Agent B2-12 and Abamectin B2-2 2 and Acetamiprid B2-3 2 and Amitraz B2-4 2 andAvermectin B2-5 2 and Azadirachtin B2-5a 2 and Bensultap B2-6 2 andBeta-cyfluthrin B2-7 2 and Bifenthrin B2-8 2 and Buprofezin B2-9 2 andCartap B2-10 2 and Chlorantraniliprole B2-11 2 and Chlorfenapyr B2-12 2and Chlorpyrifos B2-13 2 and Clothianidin B2-14 2 and CyantraniliproleB2-15 2 and Cyfluthrin B2-16 2 and Cyhalothrin B2-17 2 and CypermethrinB2-18 2 and Cyromazine B2-19 2 and Deltamethrin B2-20 2 and DieldrinB2-21 2 and Dinotefuran B2-22 2 and Diofenolan B2-23 2 and EmamectinB2-24 2 and Endosulfan B2-25 2 and Esfenvalerate B2-26 2 and EthiproleB2-27 2 and Fenothiocarb B2-28 2 and Fenoxycarb B2-29 2 and FenvalerateB2-30 2 and Fipronil B2-31 2 and Flonicamid B2-32 2 and FlubendiamideB2-33 2 and Flufenoxuron B2-34 2 and Hexaflumuron B2-35 2 andHydramethylnon B2-36 2 and Imidacloprid B2-37 2 and Indoxacarb B2-38 2and Lambda-cyhalothrin B2-39 2 and Lufenuron B2-40 2 and MetaflumizoneB2-41 2 and Methomyl B2-42 2 and Methoprene B2-43 2 and MethoxyfenozideB2-44 2 and Nitenpyram B2-45 2 and Nithiazine B2-46 2 and NovaluronB2-47 2 and Oxamyl B2-48 2 and Phosmet B2-49 2 and Pymetrozine B2-50 2and Pyrethrin B2-51 2 and Pyridaben B2-52 2 and Pyridalyl B2-53 2 andPyriproxyfen B2-54 2 and Ryanodine B2-55 2 and Spinetoram B2-56 2 andSpinosad B2-57 2 and Spirodiclofen B2-58 2 and Spiromesifen B2-59 2 andSpirotetramat B2-60 2 and Tebufenozide B2-61 2 and Thiacloprid B2-62 2and Thiamethoxam B2-63 2 and Thiodicarb B2-64 2 and Thiosultap-sodiumB2-65 2 and Tolfenpyrad B2-66 2 and Tralomethrin B2-67 2 and TriazamateB2-68 2 and Triflumuron B2-69 2 and Bacillus thuringiensis B2-70 2 andBacillus thuringiensis delta-endotoxin B2-71 2 and NPV (e.g., Gemstar)

Table B2 is identical to Table B1, except that each reference toCompound 1 in the column headed “Cmpd. No.” is replaced by a referenceto Compound 2. For example, the first mixture in Table B2 is designatedB2-1 and is a mixture of Compound 2 and the additional insect pestcontrol agent abamectin.

The specific mixtures listed in Tables B1 and B2 typically combine acompound of Formula 1 with the other invertebrate pest agent in theratios specified in Table A.

Listed below in Tables C1 and C2 are embodiments of specificcompositions comprising a compound of Formula 1 (Compound 1 is3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamideand Compound 2 is3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide)and an additional fungicide.

TABLE C1 Mixture Cmpd. No. No. and Fungicide C1-1 1 and Probenazole C1-21 and Tiadinil C1-3 1 and Isotianil C1-4 1 and Pyroquilon C1-5 1 andMetominostrobin C1-6 1 and Flutolanil C1-7 1 and Validamycin C1-8 1 andFurametpyr C1-9 1 and Pencycuron C1-10 1 and Simeconazole C1-11 1 andOrysastrobin C1-12 1 and Trifloxystrobin C1-13 1 and IsoprothiolaneC1-14 1 and Azoxystrobin C1-15 1 and Tricyclazole C1-16 1 andHexaconazole C1-17 1 and Difenoconazole C1-18 1 and Cyproconazole C1-191 and Propiconazole C1-20 1 and Fenoxanil C1-21 1 and Ferimzone C1-22 1and Fthalide C1-23 1 and Kasugamycin C1-24 1 and Picoxystrobin C1-25 1and Penthiopyrad C1-26 1 and Famoxadone C1-27 1 and Cymoxanil C1-28 1and Proquinazid C1-29 1 and Flusilazole C1-30 1 and Mancozeb C1-31 1 andCopper hydroxide C1-32 1 and (a) (a)1-[4-[4-[5-(2,6-difluoraphenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-ethanone

TABLE C2 Mixture Cmpd. No. No. and Fungicide C2-1 2 and Probenazole C2-22 and Tiadinil C2-3 2 and Isotianil C2-4 2 and Pyroquilon C2-5 2 andMetominostrobin C2-6 2 and Flutolanil C2-7 2 and Validamycin C2-8 2 andFurametpyr C2-9 2 and Pencycuron C2-10 2 and Simeconazole C2-11 2 andOrysastrobin C2-12 2 and Trifloxystrobin C2-13 2 and IsoprothiolaneC2-14 2 and Azoxystrobin C2-15 2 and Tricyclazole C2-16 2 andHexaconazole C2-17 2 and Difenoconazole C2-18 2 and Cyproconazole C2-192 and Propiconazole C2-20 2 and Fenoxanil C2-21 2 and Ferimzone C2-22 2and Fthalide C2-23 2 and Kasugamycin C2-24 2 and Picoxystrobin C2-25 2and Penthiopyrad C2-26 2 and Famoxadone C2-27 2 and Cymoxanil C2-28 2and Proquinazid C2-29 2 and Flusilazole C2-30 2 and Mencozeb C2-31 2 andCopper hydroxide C2-32 2 and (a)

Table C2 is identical to Table C1, except that each reference toCompound 1 in the column headed “Cmpd. No.” is replaced by a referenceto Compound 2. For example, the first mixture in Table C2 is designatedC2-1 and is a mixture of Compound 2 and the additional fungicideprobenazole.

As an alternative to including other biologically active agents ascomponent (d) in the present composition, other biologically activeingredients can be separately applied to propagules.

The present composition can optionally further comprise (e) up to about80% by weight of one or more inert formulating ingredients other thanpoly(lactide-co-glycolide) or (acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) triblock copolymers. As used herein, the term“inert formulating ingredient” refers to ingredients included incompositions other than the chemicals or other agents providing thebiological activity to control the intended pests (e.g., as describedfor component (d)). Such inert formulating ingredients are also known asformulation aids. When present, component (e) is typically at least 0.1%of the composition by weight. Except when the composition is intendedfor pelleting seeds, the amount of component (e) is typically not morethan about 20% of the composition by weight.

Component (e) can comprise a wide variety of inert formulatingingredients other than the provides poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersof component (c), including for example, adhesives, liquid diluents,solid diluents, surfactants (e.g., having wetting agent, dispersantand/or anti-foam properties), antifreeze agents, preservatives such aschemical stabilizers or biocides, thickening agents and fertilizers. Theprovides poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersof component (c) can function as surfactants (e.g., wetting agents,dispersants) and/or adhesives. Indeed, providespoly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymers are known for their wetting anddispersing properties, although they are generally included informulations at concentrations substantially less than specified herein.Therefore component (c) can reduce or eliminate the benefit of includingcertain additional inert formulating ingredients as constituents ofcomponent (e). Nevertheless, inclusion of ingredients such assurfactants and adhesives in component (e) may still be desirable.

In the context of the present disclosure and claims, the term “adhesive”refers to a substance capable of binding component (a) to a propagulesuch as a seed. Adhesives include substances exhibiting tackiness suchas methylcellulose or gum arabic, which are known as sticking agents.Adhesives also include substances known as film-formers, which provide adurable uniform film when applied to a surface. Although an adhesivesubstance can be included as a constituent of component (e) in thepresent composition, such inclusion is often not advantageous, becausethe provides poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersof component (c) have adhesive properties. However, including additionaladhesive substance is most likely to be advantageous when component (c)is a liquid or paste (i.e., not solid), and particularly when component(c) is a liquid.

The adhesive agent can comprise an adhesive polymer that is natural orsynthetic and is without phytotoxic effect on the seed or propagule tobe coated. The adhesive agent can be selected from the group consistingof polyvinyl acetates, polyvinyl acetate copolymers, hydrolyzedpolyvinyl acetates, polyvinylpyrrolidone-vinyl acetate copolymers,polyvinyl alcohols, polyvinyl alcohol copolymers, polyvinyl methylether, polyvinyl methyl ether-maleic anhydride copolymers, waxes, latexpolymers, celluloses including ethylcelluloses and methylcelluloses,hydroxymethylcelluloses, hydroxypropylcelluloses,hydroxymethylpropylcelluloses, polyvinylpyrrolidones, alginates,dextrins, malto-dextrins, polysaccharides, fats, oils, proteins, karayagum, jaguar gum, tragacanth gum, polysaccharide gums, mucilage, gumarabics, shellacs, vinylidene chloride polymers and copolymers, soybeanprotein-based polymers and copolymers, lignosulfonates, acryliccopolymers, starches, polyvinylacrylates, zeins, gelatin,carboxymethylcellulose, chitosan, polyethylene oxide, acrylimidepolymers and copolymers, polyhydroxyethyl acrylate, methylacrylimidepolymers, alginate, ethylcellulose, polychloroprene, and syrups ormixtures thereof. The above-identified polymers include those known inthe art, such as AGRIMER VA 6 and LICOWAX KST. Of note as adhesives arepolyvinylpyrrolidinone-vinyl acetate copolymers and water-soluble waxes(e.g., polyethylene glycol).

The total amount of adhesive (i.e., the sum of component (b), (c), andadhesives in component (e)) in the composition adhering to a coatedpropagule is generally in the range of about 0.001 to 100% of the weightof the propagule. For large seeds, the total amount of adhesive istypically in the range of about 0.05 to 5% of the seed weight; for smallseeds the total amount is typically in the range of about 1 to 100%, butcan be greater than 100% of seed weight in pelleting. For otherpropagules, the total amount of adhesive is typically in the range of0.001 to 2% of the propagule weight.

Optionally, the present composition can contain up to about 10% (basedon the weight of the composition) of liquid diluents as a constituent ofcomponent (e). In the context of the present disclosure and claims, theterm “liquid diluent” excludes water unless otherwise indicated. Whenthe present composition comprises one or more liquid diluents, theygenerally amount to at least 0.1% of the composition by weight.Typically, as a constituent in a composition coating a propagule, theliquid diluents are relatively nonvolatile, i.e., have a normal boilingpoint of greater than about 160° C., preferably greater than about 200°C. Examples of liquid diluents include N-alkylpyrrolidones, dimethylsulfoxide, ethylene glycol, polypropylene glycol, propylene carbonate,dibasic esters, paraffins, alkylnaphthalenes, oils of olive, castor,linseed, tung, sesame, corn, peanut, cottonseed, soybean, rapeseed andcoconut, fatty acid esters, ketones such as isophorone and4-hydroxy-4-methyl-2-pentanone, and alcohols such as cyclohexanol,decanol, benzyl and tetrahydrofurfuryl alcohol. Typical liquid diluentsare described in Marsden, Solvents Guide, 2nd Ed., Interscience, NewYork, 1950. As the presence of liquid diluents can soften a compositioncoating a propagule, the present composition typically comprises notmore than about 5% of liquid diluents by weight.

Optionally, the present composition can contain up to about 75% (basedon the weight of the composition) of solid diluents as a constituent ofcomponent (e). When the present composition comprises one or more soliddiluents, they generally amount to at least 0.1% of the composition byweight. In the context of the present disclosure and claims, soliddiluents are considered to be solid substances principally providingbulk instead of other useful (e.g., adhesive, surfactant) properties.Typical solid diluents are described in Watkins et al., Handbook ofInsecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books,Caldwell, N.J. Solid diluents include, for example, clays such asbentonite, montmorillonite, attapulgite and kaolin, starch, sugar,silica, talc, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. High concentrations ofsolid diluents (i.e., up to about 75%) are typically included in acomposition of the present invention for pelleting seeds. For pelletingseeds, the solid diluents are preferably insoluble, for example,bentonite, montmorillonite, attapulgite and kaolin (clays), silica(e.g., powdered silica) and calcium carbonate (e.g., ground limestone).When the present composition is not intended for pelleting seeds, theamount of solid diluents is typically not more than about 10% of thecomposition by weight.

The nanoparticle comprised of polymer/anthranilamide components (b)typically obviate the need to include additional surfactants such aswetting agents and dispersants, but one or more such surfactants can beincluded in the composition as a constituent of component (e). If thepresent composition includes additional wetting agents or dispersants,they typically are present in an amount of at least about 0.1% of thecomposition by weight. Typically, the present composition does notinclude more than about 15%, more typically not more than about 10%, andmost typically not more than about 5% of additional surfactants byweight.

Examples of dispersing agents include anionic surfactants such asphosphate esters of tristyryiphenol ethoxylates (e.g., SOPROPHOR 3D33),alkylarylsulfonic acids and their salts (e.g., SUPRAGIL MNS90), ligninsulfonates (e.g., ammonium lignosulfonate or sodium lignosulfonate),polyphenol sulfonates, polyacrylic acids, acrylic graft copolymers suchas acrylic acid/methyl methacrylate/polyoxyethylene graft copolymers(e.g., ATLOX 4913), and other polymers combining polyoxyalkylene withacid functionality such as ATLOX 4912 (a block copolymer ofpolyoxyethylene and hydroxystearic acid).

Examples of wetting agents (some of which overlap with dispersingagents) include alkyl sulfate salts (e.g., SIPON LC 98, sodium laurylsulfate), alkyl ether sulfate salts (e.g., sodium lauryl ether sulfate),alkylarylsulfonates (i.e., salts of alkylarylsulfonic acids, includingarylsulfonic acids substituted with more than one alkyl moiety) such assodium or calcium alkylbenzenesulfonates (e.g., RHODACAL DS1) andalkylnaphthalenesulfonates (e.g., RHODACAL BX-78), α-olefin sulfonatesalts, dialkyl sulfosuccinate salts and salts of polycarboxylic acids.

Additional surfactants include, for example, ethoxylated alcohols,ethoxylated alkylphenols, ethoxylated sorbitan fatty acid esters,ethoxylated sorbitol fatty acid esters, ethoxylated amines, ethoxylatedfatty acids and esters (including ethoxylated vegetable oils),organosilicones, N,N-dialkyltaurates, glycol esters, formaldehydecondensates, and block polymers other than poly(lactide-co-glycolide)(or acrylate/methacrylate-based)/methylated poly(ethylene glycol)copolymers.

Component (e) can also comprise one or more anti-foaming agents.Anti-foaming agents are surfactants that can effectively either preventfoam formation or reduce or eliminate it once it has formed. Examples ofanti-foaming agents include silicone oils, mineral oils,polydialkylsiloxanes such as polydimethylsiloxanes, fatty acids andtheir salts with polyvalent cations such as calcium, magnesium andaluminum, alkyne diols (e.g., SURFYNOL 104), and fluoroaliphatic esters,perfluoroalkylphosphonic and perfluoroalkylphosphinic acids, and saltsthereof. When the present composition comprises one or more anti-foamingagents, they typically amount to at least about 0.01% and not more thanabout 3% of the composition by weight. More typically, anti-foamingagents are not more than about 2% and most typically not more than about1% of the composition by weight.

McCutcheon's Emulsifiers and Detergents and McCutcheon's FunctionalMaterials (North America and International Editions, 2001), TheManufacturing Confection Publ. Co., Glen Rock, N.J., as well as Siselyand Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co.,Inc., New York, 1964, list surfactants and recommended uses.

Component (e) can comprise one or more antifreeze agents. Antifreezeagents prevent freezing of the composition of the present inventionextended with an aqueous liquid carrier before coating on propagules.Examples of antifreeze agents include glycols such as ethylene glycol,diethylene glycol, propylene glycol, dipropylene glycol, glycerol,1,3-propanediol, 1,2-propanediol and polyethylene glycol of molecularweight in the range from about 200 to about 1,000 daltons. Antifreezeagents of note for the composition of the present invention includeethylene glycol, propylene glycol, glycerol, 1,3-propanediol and1,2-propanediol. When component (e) comprises one or more antifreezeagents, they typically amount to at least about 0.1% and not more thanabout 14% of the composition by weight. More typically, antifreezeagents do not amount to more than 10% and most typically not more thanabout 8% of the total weight of the composition.

Component (e) can comprise one or more thickening agents. Thickeningagents (i.e., thickeners) increase the viscosity of the continuousliquid medium formed when the present composition is extended with anaqueous liquid carrier. By increasing viscosity, the propensity of solidparticles (e.g., of component (a)) to settle is reduced. Becausecomponents (b) and (c) also increase viscosity, including one or morethickening agents in component (e) is generally not necessary and indeedcan be unhelpful if the viscosity of the composition is already as muchas desired. Including one or more thickening agents in component (e) canbe beneficial for slowing settling of particles of component (a) if thecomposition is extended with a large amount of aqueous liquid carrierrelative to component (b) and (c), particularly when component (b) and(c) comprises mainly provides poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersof relatively low molecular weight (i.e., less than about 17,000daltons). Examples of thickening agents useful for the presentcomposition include polyols such as glycerol, polysaccharides includingheteropolysaccharides such as xanthan gum, and hydrated clays with verysmall particle sizes (e.g., 2 nm) such as the hydrated magnesiumaluminosilicate ACTI-GEL 208 (Active Minerals). Glycerol is of note ashaving both antifreeze and thickener properties. An extensive list ofthickeners and their applications can be found in McCutcheon's 2005,Volume 2: Functional Materials published by MC Publishing Company. Ifcomponent (e) comprises one or more thickening agents, they typicallyamount to at least about 0.1% and not greater than about 5% of thecomposition by weight.

Component (e) can comprise a preservative constituent consistingessentially of one or more stabilizing agents or biocides, and theamount of the preservative constituent is typically up to about 1% ofthe composition by weight. When a preservative constituent is present,it typically amounts to at least about 0.01% of the composition byweight. The preservative constituent does not exceed typically about 1%,more typically about 0.5% and most typically about 0.3% of the totalweight of the composition.

Stabilizing agents, for example, anti-oxidants (such asbutylhydroxytoluene) or pH modifiers (such as citric acid or aceticacid) can prevent decomposition of active ingredients (i.e., component(a) and/or component (d)) during storage. Biocides can prevent or reducemicrobial contamination within a formulated composition. Particularlysuitable biocides are bactericides such as LEGEND MK (a mixture of5-chloro-2-methyl-3(2H)-isothiazolone with2-methyl-3(2H)-isothiazolone), EDTA (ethylenediaminetetraacetic acid),formaldehyde, benzoic acid, and 1,2-benzisothiazol-3(2H)-one or itssalts (e.g., PROXEL BD or PROXEL GXL (Arch Chemicals, Inc.)). Of note isthe present composition wherein component (e) comprises a biocide, inparticular, a bactericide such as 1,2-benzisothiazol-3(2H)-one or one ofits salts.

Component (e) can also comprise one or more fertilizers. Fertilizersincluded in component (e) can provide plant nutrients such as nitrogen,phosphorus and potassium and/or micronutrients such as manganese, iron,zinc and molybdenum. Of note for inclusion in component (e) aremicronutrients such as manganese, iron, zinc and molybdenum. If one ormore fertilizers are present, they typically amount to at least about0.1% and not more than about 20% of the composition by weight, althoughgreater amounts can be included.

Other formulation ingredients can be included in the present compositionas component (e), such as rheology modifiers, dyes, and the like. Theseingredients are known to one skilled in the art and can be founddescribed, for example, in McCutcheon's, Volume 2: Functional Materialspublished by MC Publishing Company annually.

One aspect of the present invention is a geotropic propagule coated withan insecticidally effective amount of the aforedescribed composition.Geotropic propagules include seeds. The present invention is applicableto virtually all seeds, including seeds of wheat (Triticum aestivum L.),durum wheat (Triticum durum Desf.), barley (Hordeum vulgare L.), oat(Avena sativa L.), rye (Secale cereale L.), maize (Zea mays L.), sorghum(Sorghum vulgare Pers.), rice (Oryza sativa L.), wild rice (Zizaniaaquatica L.), cotton (Gossypium barbadense L. and G. hirsutum L.), flax(Linum usitatissimum L.), sunflower (Helianthus annuus L.), soybean(Glycine max Merr.), garden bean (Phaseolus vulgaris L.), lima bean(Phaseolus limensis Macf.), broad bean (Vicia faba L.), garden pea(Pisum sativum L.), peanut (Arachis hypogaea L.), alfalfa (Medicagosativa L.), beet (Beta vulgaris L.), garden lettuce (Lactuca sativa L.),rapeseed (Brassica rapa L. and B. napus L.), cole crops such as cabbage,cauliflower and broccoli (Brassica oleracea L.), turnip (Brassica rapaL.), leaf (oriental) mustard (Brassica juncea Coss.), black mustard(Brassica nigra Koch), tomato (Lycopersicon esculentum Mill.), potato(Solanum tuberosum L.), pepper (Capsicum frutescens L.), eggplant(Solanum melongena L.), tobacco (Nicotiana tabacum), cucumber (Cucumissativus L.), muskmelon (Cucumis melo L.), watermelon (Citrullus vulgarisSchrad.), squash (Curcurbita pepo L., C. moschata Duchesne, and C.maxima Duchesne.), carrot (Daucus carota L.), zinnia (Zinnia elegansJacq.), cosmos (e.g., Cosmos bipinnatus Cav.), chrysanthemum(Chrysanthemum spp.), sweet scabious (Scabiosa atropurpurea L.),snapdragon (Antirrhinum majus L.), gerbera (Gerbera jamesonii Bolus),babys-breath (Gypsophila paniculata L., G. repens L. and G. elegansBieb.), statice (e.g., Limonium sinuatum Mill., L. sinense Kuntze.),blazing star (e.g., Liatris spicata Willd., L. pycnostachya Michx., L.scariosa Willd.), lisianthus (e.g., Eustoma grandiflorum (Raf.) Shinn),yarrow (e.g., Achillea filipendulina Lam., A. millefolium L.), marigold(e.g., Tagetes patula L., T. erecta L.), pansy (e.g., Viola comuta L.,V. tricolor L.), impatiens (e.g., Impatiens balsamina L.), petunia(Petunia spp.), geranium (Geranium spp.) and coleus (e.g., Solenostemonscutellarioides (L.) Codd). Geotropic propagules also include rhizomes,tubers, bulbs or corms, or viable divisions thereof. Suitable rhizomes,tubers, bulbs and corms, or viable divisions thereof include those ofpotato (Solanum tuberosum L.), sweet potato (Ipomoea batatas L.), yam(Dioscorea cayenensis Lam. and D. rotundata Poir.), garden onion (e.g.,Allium cepa L.), tulip (Tulipa spp.), gladiolus (Gladiolus spp.), lily(Lilium spp.), narcissus (Narcissus spp.), dahlia (e.g., Dahlia pinnataCav.), iris (Iris germanica L. and other species), crocus (Crocus spp.),anemone (Anemone spp.), hyacinth (Hyacinth spp.), grape-hyacinth(Muscari spp.), freesia (e.g., Freesia refracta Klatt., F. armstrongiiW. Wats), ornamental onion (Allium spp.), wood-sorrel (Oxalis spp.),squill (Scilla peruviana L. and other species), cyclamen (Cyclamenpersicum Mill. and other species), glory-of-the-snow (Chionodoxaluciliae Boiss. and other species), striped squill (Puschkiniascilloides Adams), calla lily (Zantedeschia aethiopica Spreng., Z.elliottiana Engler and other species), gloxinia (Sinnigia speciosaBenth. & Hook.) and tuberous begonia (Begonia tuberhybrida Voss.). Theabove recited cereal, vegetable, omamental (including flower) and fruitcrops are illustrative, and should not be considered limiting in anyway. For reasons of insect control spectrum and economic importance,embodiments coating seeds of cotton, maize, soybean, rapeseed and rice,and coating tubers and bulbs of potato, sweet potato, garden onion,tulip, daffodil, crocus and hyacinth are of note. Also of note areembodiments wherein the geotropic propagule is a seed.

The present composition can be coated on geotropic propagules thatcontain genetic material introduced by genetic engineering (i.e.,transgenic) or modified by mutagenesis to provide advantageous traits.Examples of such traits include tolerance to herbicides, resistance tophytophagous pests (e.g., insects, mites, aphids, spiders, nematodes,snails, plant-pathogenic fungi, bacteria and viruses), improved plantgrowth, increased tolerance of adverse growing conditions such as highor low temperatures, low or high soil moisture, and high salinity,increased flowering or fruiting, greater harvest yields, more rapidmaturation, higher quality and/or nutritional value of the harvestedproduct, or improved storage or process properties of the harvestedproducts. Transgenic plants can be modified to express multiple traits.Examples of plants containing traits provided by genetic engineering ormutagenesis include varieties of corn, cotton, soybean and potatoexpressing an insecticidal Bacillus thuringiensis toxin such as YIELDGARD, KNOCKOUT, STARLINK, BOLLGARD, NuCOTN and NEWLEAF, andherbicide-tolerant varieties of corn, cotton, soybean and rapeseed suchas ROUNDUP READY, LIBERTY LINK, IMI, STS and CLEARFIELD, as well ascrops expressing N-acetyltransferase (GAT) to provide resistance toglyphosate herbicide, or crops containing the HRA gene providingresistance to herbicides inhibiting acetolactate synthase (ALS). Thepresent insecticidal composition may interact synergistically withtraits introduced by genetic engineering or modified by mutagenesis,thus enhancing phenotypic expression or effectiveness of the traits orincreasing the insect control effectiveness of the present composition.In particular, the present insecticidal composition may interactsynergistically with the phenotypic expression of proteins or othernatural products toxic to invertebrate pests to providegreater-than-additive control of these pests.

The thickness of coatings of the present composition on geotropicpropagules can vary from thin films 0.001 mm thick to layers about 0.5to 5 mm thick. Generally, a coating that increases the weight of a seedup to 25% is defined as a film coating. Film-coated seed retains theshape and the general size of the uncoated seed. A coating thatincreases the weight of the seed more than 25% is referred to as apellet coating. Coatings on geotropic propagules can comprise more thanone adhering layer, only one of which need comprise the presentcomposition. Generally pellets are more satisfactory for small seeds,because their ability to provide an insecticidally effective amount ofthe present composition is not limited by the surface area of the seed,and pelleting small seeds also facilitates seed transfer and plantingoperations. Because of their larger size and surface area, large seedsand bulbs, tubers, corms and rhizomes and their viable cuttings aregenerally not pelleted, but instead coated with a thin film.

For application of a coating of the aforedescribed composition to ageotropic propagule, the composition is typically first extended with avolatile aqueous liquid carrier to provide a liquid compositionconsisting of about 5 to 80 weight % of the aforedescribed (unextended)composition (i.e., mixture comprising components (a), (b), (c), andoptionally (d) and (e)) and about 20 to 95 weight % of the volatileaqueous liquid carrier. Alternatively and more typically, one or more ofthe composition components is first mixed with the volatile aqueousliquid carrier before the components are combined to provide the liquidcomposition containing components (a), (b), (c), and optionally (d) and(e) in combination with about 20-95 weight % of the volatile aqueousliquid carrier. The amount of volatile liquid carrier is more typicallyat least about 25% and most typically at least about 30% of the liquidcomposition by weight. Also, the amount of volatile liquid carrier ismore typically not more than about 70% of the liquid composition byweight.

In the context of the present disclosure and claims, the expression“volatile aqueous liquid carrier” refers to a composition consisting ofat least about 50% water by weight and optionally one or morewater-soluble compounds that are liquid at 20° C. and have a normalboiling point of not greater than about 100° C. These water-solubleliquid compounds should be nonphytotoxic to the geotropic propagule tobe coated. Examples of such water-soluble liquid compounds are acetone,methyl acetate, methanol and ethanol. However, a volatile aqueous liquidcarrier mostly or entirely of water is typically preferable, becausewater is inexpensive, nonflammable, environmentally friendly andnonphytotoxic. Typically, the volatile aqueous liquid carrier comprisesat least about 80%, more typically at least about 90%, and mosttypically at least about 95% water by weight. In some embodiments, thevolatile aqueous liquid carrier consists essentially of water. In someembodiments, the volatile liquid carrier is water.

In the liquid composition comprising the volatile aqueous liquidcarrier, the volatile aqueous liquid carrier forms a continuous liquidphase in which other components (e.g., components (a), (b), (c), andoptionally (d) and (e)) are suspended or dissolved. Typically, at leastsome of components (a) and (b) are present as particles suspended in thecontinuous liquid phase and therefore the liquid composition can bedescribed as a suspension concentrate composition. In some embodimentsat least about 90%, or 95% or 98% of components (a) and (b) are presentas particles suspended in the continuous liquid phase. Typically, morethan 95% by weight of the particles have a particle size less than about10 microns.

The aggregation state of the poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymerscomponent (i.e., component (c)) in the liquid composition depends onsuch parameters as ingredients, concentration, temperature and ionicstrength. The liquid composition typically comprises suspended particlesof components (a) and (b) having large surface areas.Poly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymer molecules are generally adsorbed to suchinterfaces (e.g., as monolayers, bilayers or hemimicelles) in preferenceto remaining in solution, and only when the interfaces are saturated dohigh concentrations of the molecules remain in the aqueous phase.Therefore the presence of particles of component (a) and (b) allows theliquid composition to accommodate more of component (c) without forminga separate component (c) phase than would be expected based solely onwater solubility. If the liquid composition contains component (c) inexcess of both its adsorption onto component (a) and (b) particles andits solubility in the aqueous carrier phase, a portion of component (c)will be present in a discrete phase, either as solid particles or asliquid droplets depending upon the physical properties (e.g., meltingpoint) of component (c).

The liquid composition comprising the volatile aqueous liquid carrier isoften most conveniently prepared by mixing components (a), (b), (c) andoptionally (d) and (e) with the volatile aqueous liquid carrier (e.g.,water). As noted above, component (c) is water-soluble to the extent ofat least 5% at 20° C. For ease of dissolution of component (c) in theformulation, it is preferred to dissolve components (c) in the aqueousliquid carrier prior to mixing with the other ingredients.

In the liquid composition, the median particle size of particles ofcomponent (a) is preferably less than about 180 nm to provide goodsuspensibility as well as high biological availability and coatingcoverage of the propagule. More preferably the median particle size ofcomponent (a) is less than 200 nm or 150 nm or 125 nm and mostpreferably less than about 100 nm. Typically, the median particle sizeis at least about 100 nm, but smaller particle sizes are suitable.

Milling can be used to reduce the particle size of component (a) as wellas other solid components. Milling methods are well-known and includeball-milling, bead-milling, sand-milling, colloid-milling andair-milling. These can be combined with high-speed blending, whichtypically involves high shear, to prepare suspensions and dispersions ofparticles. Of particular note is ball- or bead-milling for reducing theparticle size of component (a). Other components, such as component (b)or (c), can be included in the mixture for milling or later mixed withthe milled mixture. However, other components comprising solid particlesinitially having a particle size of greater than 10 microns and lowwater solubility are typically included in the mixture for milling.Although poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymercomponent (b) or (c) and optional additional surfactant of component (e)can be added after milling component (a), typically a portion ofcomponent (c) and/or optional additional surfactant is included in themixture to facilitate milling component (a) to small particle size.

Milling is often unneeded in methods for preparing the liquidcomposition by first dissolving component (a) in an organic solvent. Inone method, components (a), (b), and (c) and optionally other componentsare dissolved in an organic solvent, and then a miscible solvent inwhich components (a), (b), and (c) are much less soluble is added to thesolution of components (a), (b), and (c) to form a precipitate. Theprecipitate is collected and suspended in the volatile aqueous liquidcarrier (e.g., water) for coating propagules. N-methyl-2-pyrrolidone anddiethyl ether are suitable as the more soluble and less solublesolvents, respectively, when the poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymersof component (c) have a high polyoxyethylene content (e.g., about 80% orgreater), thus causing low solubility in diethyl ether.

In a related method, components (a), (b), and (c) and optionally othercomponents are dissolved in an organic solvent system comprising a lowerboiling solvent in which component (a) is very soluble and a higherboiling solvent in which component (a) is less soluble (e.g., a binarysolvent system of dichloromethane and ethanol), and then the solvent isevaporated under vacuum. The residue is then suspended in the volatileaqueous liquid carrier (e.g., water) for coating propagules.

In another method, component (a) and (b) and component (c) are dissolvedin a water-miscible organic solvent such as N-methyl-2-pyrrolidone. Thesolution is then placed inside a sealed dialysis membrane, which isselected to allow the organic solvent and water to equilibrate but notallow passage of component (c). The sealed dialysis membrane is thenplaced in water to allow replacement of the organic solvent with water.Water entering the dialysis membrane causes component (a) to crystallizeand form a slurry. The resultant aqueous slurry is used to coatpropagules.

After the liquid composition comprising the volatile aqueous liquidcarrier has been prepared, it can be applied to the surface of apropagule by any of several techniques known in the art, which involveevaporating the volatile aqueous liquid carrier to leave a coating ofthe insecticidal composition comprising components (a), (b), (c), andoptionally (d) and (e) adhering to the surface of the propagule. Variouscoating machines and processes are available to one skilled in the art.Suitable processes include those listed in P. Kosters et al., SeedTreatment: Progress and Prospects, 1994 BCPC Monograph No. 57 and thereferences listed therein. Coating processes are also described in U.S.Pat. Nos. 5,527,760 and 6,202,345. Three well-known techniques includethe use of drum coaters, fluidized bed techniques and spouted beds.Seeds can be presized prior to coating. After coating, the seeds aredried and then optionally sized by transfer to a sizing machine. Thesemachines are known in the art.

In one method, propagules are coated by spraying the liquid compositioncomprising the volatile aqueous liquid carrier directly into a tumblingbed of seeds and then drying the propagules. In one embodiment forcoating seeds, the seed and coating material are mixed in a conventionalseed coating apparatus. The rate of rolling and application of coatingdepends upon the seed. For large oblong seeds such as that of cotton, asatisfactory seed coating apparatus comprises a rotating type pan withlifting vanes turned at sufficient rpm to maintain a rolling action ofthe seed, facilitating uniform coverage. The seed coating must beapplied over sufficient time to allow drying to minimize clumping of theseed. Using forced air or heated forced air can allow increasing therate of application. One skilled in the art will also recognize thatthis process may be a batch or continuous process. As the name implies,a continuous process allows the seeds to flow continuously throughoutthe product run. New seeds enter the pan in a steady stream to replacecoated seeds exiting the pan.

One embodiment of seed coating is seed pelleting. The pelleting processtypically increases the seed weight from 2 to 100 times and can be usedto also improve the shape of the seed for use in mechanical seeders.Pelleting compositions generally contain a solid diluent, which istypically an insoluble particulate material, such as clay, groundlimestone, or powdered silica to provide bulk in addition to afilm-former or sticking agent. Depending on the extent of coatingapplied, pelletizing may provide a spherical shape to the seeds whichare normally elongated or irregularly shaped. A method for producingpellets is described in Agrow, The Seed Treatment Market, Chapter 3, PJBPublications Ltd., 1994.

One aspect of the present invention is a method for protecting ageotropic propagule and plant derived therefrom from a phytophagousinsect pest by coating the propagule with an insecticidally effectiveamount of the liquid composition comprising components (a), (b), (c) andoptionally (d) and (e) along with a volatile aqueous liquid carrier andthen evaporating the volatile aqueous liquid carrier of the composition.This coating process constitutes a treatment of the propagule byproviding a coating of an insecticidally effective amount of theinsecticidal composition on the propagule. The coating of thecomposition on the propagule provides an insecticidally effective amountof component (a) (i.e., one or more anthranilic diamide insecticides)available for absorption into the propagule and/or roots developing fromthe propagule. In some embodiments, the poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymerof component (b) and (c) have been discovered to increase the absorptionof component (a) into the propagules and/or developing roots to providethrough xylem transport an insecticidally effective concentration ofcomponent (a) in even foliage developing from the coated propagule.Sufficiently increasing the absorption can raise concentrations ofcomponent (a) above the minimum concentration for insecticidaleffectiveness in not only the lower foliage but also middle to upperfoliage, and provide protection later into the growing season.Insecticidally effective concentrations of component (a) protect thepropagule and derived plant from injury or damage caused by aphytophagous insect pest by controlling the insect pest. This controlcan include killing the insect pest, interfering with its growth,development or reproduction, and/or inhibiting its feeding. Typically,control involves feeding inhibition and death of the insect pest.

Generally to protect a seed and foliage developing therefrom from aphytophagous insect pest, the present composition is coated on ageotropic propagule to provide component (a) in an amount ranging fromabout 0.001 to 50% of the weight of the propagule, for seeds more oftenin the range of about 0.01 to 50% of the seed weight, and most typicallyfor large seeds in the range of about 0.01 to 10% of the seed weight.However, larger amounts up to about 100% or more are useful,particularly for pelleting small seed for extended invertebrate pestcontrol protection. For propagules such as bulbs, tubers, corms andrhizomes and their viable cuttings, generally the amount of component(a) included in the composition coating ranges from about 0.001 to 5% ofthe propagule weight, with the higher percentages used for smallerpropagules. One skilled in the art can easily determine theinsecticidally effective amount of the present composition and component(a) necessary for the desired level of phytophagous insect pest controland seed and plant protection.

As referred to in this disclosure, the term “phytophagous insect pest”includes larvae of the order Lepidoptera, such as armyworms, cutworms,loopers, and heliothines in the family Noctuidae (e.g., fall armyworm(Spodoptera fugiperda J. E. Smith), beet armyworm (Spodoptera exiguaHübner), black cutworm (Agrotis ipsilon Hufnagel), cabbage looper(Trichoplusia ni Hübner), and tobacco budworm (Heliothis virescensFabricius)); borers, casebearers, webworms, coneworms, cabbageworms andskeletonizers from the family Pyralidae (e.g., European corn borer(Ostrinia nubilalis Hübner), navel orangeworm (Amyelois transitellaWalker), corn root webworm (Crambus caliginosellus Clemens), and sodwebworm (Herpetogramma licarsisalis Walker)); leafrollers, budworms,seed worms, and fruit worms in the family Tortricidae (e.g., codlingmoth (Cydia pomonella L. (L. means Linnaeus)), grape berry moth(Endopiza viteana Clemens), and oriental fruit moth (Grapholita molestaBusck)); and many other economically important lepidoptera (e.g.,diamondback moth (Plutella xylostella L. of family Plutellidae), pinkbollworm (Pectinophora gossypiella Saunders of family Gelechiidae), andgypsy moth (Lymantria dispar L. of family Lymantriidae)); foliar feedinglarvae and adults of the order Coleoptera including weevils from thefamilies Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil(Anthonomus grandis Boheman), rice water weevil (Lissorhoptrusoryzophilus Kuschel), and rice weevil (Sitophilus oryzae L.)); fleabeetles, cucumber beetles, rootworms, leaf beetles, potato beetles, andleafminers in the family Chrysomelidae (e.g., Colorado potato beetle(Leptinotarsa decemlineata Say), and western corn rootworm (Diabroticavirgifera virgifera LeConte)); chafers and other beetles from the familyScaribaeidae (e.g., Japanese beetle (Popillia japonica Newman) andEuropean chafer (Rhizotrogus majalis Razoumowsky)); wireworms from thefamily Elateridae and bark beetles from the family Scolytidae; adultsand larvae of the order Dermaptera including earwigs from the familyForficulidae (e.g., European earwig (Forficula auricularia L.) and blackearwig (Chelisoches morio Fabricius)); adults and nymphs of the ordersHemiptera and Homoptera such as, plant bugs from the family Miridae,cicadas from the family Cicadidae, leafhoppers (e.g., Empoasca spp.)from the family Cicadellidae, planthoppers from the families Fulgoroidaeand Delphacidae, treehoppers from the family Membracidae, psyllids fromthe family Psyllidae, whiteflies from the family Aleyrodidae, aphidsfrom the family Aphididae, phylloxera from the family Phylloxeridae,mealybugs from the family Pseudococcidae, scales from the familiesCoccidae, Diaspididae and Margarodidae, lace bugs from the familyTingidae, stink bugs from the family Pentatomidae, cinch bugs (e.g.,Blissus spp.) and other seed bugs from the family Lygaeidae, spittlebugsfrom the family Cercopidae, squash bugs from the family Coreidae, andred bugs and cotton stainers from the family Pyrrhocoridae; adults andimmatures of the order Orthoptera including grasshoppers, locusts andcrickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipesFabricius and M. differentialis Thomas), American grasshoppers (e.g.,Schistocerca americana Drury), desert locust (Schistocerca gregariaForskal), migratory locust (Locusta migratoria L.), and mole crickets(Gryllotalpa spp.)); adults and immatures of the order Diptera,including leafminers, midges, fruit flies (Tephritidae), frit flies(e.g., Oscinella frit L.), soil maggots and other Nematocera; adults andimmatures of the order Thysanoptera including onion thrips (Thripstabaci Lindeman) and other foliar feeding thrips. Of note is the presentmethod for protecting a propagule or plant derived therefrom from aphytophagous insect pest wherein the insect pest is in a taxonomic orderselected from Hemiptera (particularly the families Aleyrodidae,Aphidadae, Cicadellidae, and Delphacidae) and Lepidoptera (particularlythe families Gelechiidae, Lymantriidae, Noctuidae, Plutellidae,Pyralidae and Torticidae). Of particular note is the present methodwherein the insect pest is in the family Noctuidae.

Embodiments of the present invention include:

Embodiment 1

The insecticidal composition described in the Summary of the Inventioncomprising by weight based on the total weight of the composition:

-   -   (a) from about 0.25 to about 25% of one or more anthranilic        diamide insecticides; and    -   (b) from about 2.5 to about 25% of a poly(lactic acid) polymer        component having a water dispersabilitiy of at least about 5% by        weight at 20° C. and an average molecular weight ranging from        about 700 to about 4,000 daltons;    -   wherein the ratio of component (b) to component (a) is about 1:1        to about 1:10 by weight.    -   (c) from about 20 to about 50% of a        poly(lactide-co-glycolide)(or acrylate/methacrylate-based        polymer)/methyl poly(ethylene glycol) copolymer having a water        solubility of at least about 5% by weight at 20° C., a        hydrophilic-lipophilic balance value of at least about 7, and an        average molecular weight ranging from 12,000 to 65,000 wherein        the ratio of poly(lactide-co-glycolide) or        acrylate/methacrylate-based

Embodiment 2

The composition of Embodiment 1 wherein component (a) (i.e., one or moreanthranilic diamide insecticides) comprises at least one compoundselected from anthranilic diamides of Formula 1, N-oxides, and saltsthereof,

wherein

X is N, CF, CCl, CBr or Cl;

R¹ is CH₃, Cl, Br or F;

R² is H, F, Cl, Br or —CN;

R³ is F, Cl, Br, C₁-C₄ haloalkyl or C₁-C₄ haloalkoxy;

R^(4a) is H, C₁-C₄ alkyl, cyclopropylmethyl or 1-cyclopropylethyl;

R^(4b) is H or CH₃;

R⁵ is H, F, Cl or Br; and

R⁶ is H, F, Cl or Br.

It is noteworthy that Yang and Sun (CN101607940, 2009) disclosedpreparations of benzamide derivatives as insecticides useful for killingarthropods wherein X is C. Therefore, in addition to species whereinX═N, species of insecticides based on X═C, substituted or unsubstitutedare encompassed by the invention embodiments disclosed herein.

Embodiment 3

The composition of Embodiment 2 wherein component (a) is selected fromanthranilic diamides of Formula 1, N-oxides, and salts thereof.

Embodiment 4

The composition of Embodiment 3 wherein component (a) is selected fromanthranilic diamides of Formula 1 and salts thereof.

Embodiment 5

The composition of Embodiment 4 wherein component (a) is selected fromanthranilic diamides of Formula 1.

Embodiment 6

The composition of any one of Embodiments 2 through 5 wherein X is N; R¹is CH₃; R² is Cl or —CN; R³ is Cl, Br or CF₃; R^(4a) is C₁-C₄ alkyl;R^(4b) is H; R⁵ is Cl; and R⁶ is H.

Embodiment 7

The composition of Embodiment 6 wherein R^(4a) is CH₃ or CH(CH₃)₂.

Embodiment 8

The composition of Embodiment 7 wherein R³ is Br; and R^(4a) is CH₃(i.e., the compound of Formula 1 is chlorantraniliprole orcyantraniliprole, or optionally an N-oxide or salt thereof).

Embodiment 9

The composition of Embodiment 8 wherein R² is Cl (i.e., the compound ofFormula 1 is chlorantraniliprole, or optionally an N-oxide or saltthereof).

Embodiment 10

The composition of Embodiment 8 wherein R² is —CN (i.e., the compound ofFormula 1 is cyantraniliprole, or optionally an N-oxide or saltthereof).

Embodiment 11

The composition of any one of Embodiments 1 through 10 wherein component(a) is at least about 10% of the composition by weight.

Embodiment 12

The composition of Embodiment 11 wherein component (a) is at least about20% of the composition by weight.

Embodiment 13

The composition of Embodiment 12 wherein component (a) is at least about30% of the composition by weight.

Embodiment 14

The composition of Embodiment 13 wherein component (a) is at least about40% of the composition by weight.

Embodiment 15

The composition of any one of Embodiments 1 through 14 wherein component(a) is not more than about 90% of the composition by weight.

Embodiment 16

The composition of Embodiment 15 wherein component (a) is not more thanabout 80% of the composition by weight.

Embodiment 17

The composition of Embodiment 16 wherein component (a) is not more thanabout 70% of the composition by weight.

Embodiment 18

The composition of any one of Embodiments 1 through 17 wherein not morethan about 30% of component (a) is present in the composition as solidparticles having a particle size greater than about 10 microns.

Embodiment 19

The composition of Embodiment 18 wherein not more than about 20% ofcomponent (a) is present in the composition as solid particles having aparticle size greater than about 10 microns.

Embodiment 20

The composition of Embodiment 20 wherein not more than about 10% ofcomponent (a) is present in the composition as solid particles having aparticle size greater than about 10 microns.

Embodiment 21

The composition of any one of Embodiments 1 through 20 wherein component(c) (i.e., the poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymerscomponent) has a water solubility of at least about 10% at 20° C.

Embodiment 22

The composition of Embodiment 21 wherein component (c) has a watersolubility of at least about 25% at 20° C.

Embodiment 23

The composition of any one of Embodiments 1 through 22 wherein component(c) has a hydrophilic-lipophilic balance (HLB) value of at least about6.

Embodiment 24

The composition of Embodiment 23 wherein component (c) has an HLB valueof at least about 7.

Embodiment 25

The composition of Embodiment 24 wherein component (c) has an HLB valueof at least about 8.

Embodiment 26

The composition of Embodiment 25 wherein component (c) has an HLB valueof at least about 10.

Embodiment 27

The composition of Embodiment 26 wherein component (c) has an HLB valueof at least about 20.

Embodiment 28

The composition of Embodiment 27 wherein component (c) has an HLB valueof at least about 22.

Embodiment 29

The composition of any one of Embodiments 1 through 28 wherein component(c) has an HLB value of not more than about 40.

Embodiment 30

The composition of Embodiment 29 wherein component (c) has an HLB valueof not more than about 35.

Embodiment 31

The composition of Embodiment 30 wherein component (c) has an HLB valueof not more than about 31.

Embodiment 32

The composition of any one of Embodiments 1 through 27 wherein component(c) has an HLB value of not more than about 20.

Embodiment 33

The composition of any one of Embodiments 1 through 26 wherein component(c) has an HLB value of not more than about 15.

Embodiment 34

The composition of any one of Embodiments 1 through 33 wherein component(c) (separate from the composition) is a paste or solid at 20° C.

Embodiment 35

The composition of any one of Embodiments 1 through 32 wherein component(c) (separate from the composition) is a solid at 20° C.

Embodiment 36

The composition of any one of Embodiments 1 through 35 whereincomponents (b) and (c) have an average molecular weight of at leastabout 4,000 daltons.

Embodiment 37

The composition of Embodiment 36 wherein components (b) and (c) have anaverage molecular weight of at least about 10,000 daltons.

Embodiment 38

The composition of Embodiment 37 wherein components (b) and (c) have anaverage molecular weight of at least about 15,000 daltons.

Embodiment 39

The composition of Embodiment 38 wherein components (b) and (c) have anaverage molecular weight of at least about 20,000 daltons.

Embodiment 40

The composition of any one of Embodiments 1 through 36 whereincomponents (b) and (c) has an average molecular weight of not more thanabout 3,000 daltons.

Embodiment 41

The composition of Embodiment 37 wherein components (b) and (c) have anaverage molecular weight of not more than about 2,000 daltons.

Embodiment 42

The composition of any one of Embodiments 1 through 41 wherein component(b) (i.e. polylactic acid component) and (c) (i.e.poly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymers) are at least about 10% of thecomposition by weight.

Embodiment 43

The composition of Embodiment 42 wherein components (b) and (c) are atleast about 15% of the composition by weight.

Embodiment 44

The composition of Embodiment 43 wherein components (b) and (c) are atleast about 20% of the composition by weight.

Embodiment 45

The composition of Embodiment 44 wherein components (b) and (c) are atleast about 25% of the composition by weight.

Embodiment 46

The composition of Embodiment 45 wherein components (b) and (c) are atleast about 30% of the composition by weight.

Embodiment 47

The composition of Embodiment 46 wherein components (b) and (c) are atleast about 35% of the composition by weight.

Embodiment 48

The composition of Embodiment 47 wherein component (b) and (c) are atleast about 40% of the composition by weight.

Embodiment 49

The composition of any one of Embodiments 1 through 48 whereincomponents (b) and (c) are not more than about 80% of the composition byweight.

Embodiment 50

The composition of Embodiment 49 wherein components (b) and (c) are notmore than about 70% of the composition by weight.

Embodiment 51

The composition of Embodiment 50 wherein components (b) and (c) are notmore than about 60% of the composition by weight.

Embodiment 52

The composition of Embodiment 51 wherein components (b) and (c) are notmore than about 50% of the composition by weight.

Embodiment 53

The composition of Embodiment 52 wherein components (b) and (c) are notmore than about 40% of the composition by weight.

Embodiment 54

The composition of any one of Embodiments 1 through 53 wherein the ratioof components (b) and (c) to component (a) is at least about 30:1 (byweight).

Embodiment 55

The composition of Embodiment 54 wherein the ratio of components (b) and(c) to component (a) is at least about 100:1.

Embodiment 56

The composition of Embodiment 55 wherein the ratio of components (b) and(c) to component (a) is at least about 300:1.

Embodiment 57

The composition of Embodiment 56 wherein the ratio of component (b) tocomponent (a) is at least about 1,000:1.

Embodiment 58

The composition of any one of Embodiment 54 through 57 wherein the ratioof component (b) to component (c) is at least about 1:2.

Embodiment 59

The composition of Embodiment 58 wherein the ratio of component (b) tocomponent (c) is at least about 1:4.

Embodiment 60

The composition of Embodiment 59 wherein the ratio of component (b) tocomponent (c) is at least about 1:5.

Embodiment 61

The composition of Embodiment 60 wherein the ratio of component (b) tocomponent (c) is at least about 1:6.

Embodiment 62

The composition of Embodiment 61 wherein the ratio of component (b) tocomponent (c) is at least about 1:7.

Embodiment 63

The composition of Embodiment 62 wherein the ratio of component (b) tocomponent (c) is at least about 1:9.

Embodiment 64

The composition of any one of Embodiments 1 through 59 wherein the ratioof component (b) and (c) to component (a) is not more than about 1:1.

Embodiment 65

The composition described in the Summary of the Invention or any one ofEmbodiments 1 through 64 wherein component (b) comprises one or morepolylactic acid polymers and component (c) poly(lactide-co-glycolide)(or acrylate/methacrylate-based)/methylated poly(ethylene glycol)copolymers.

Embodiment 66

The composition of Embodiment 65 wherein component (c) comprises one ormore poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol)copolymers.

Embodiment 67

The composition of Embodiment 65 or 66 wherein component (c) comprisesone or more poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol)copolymers.

Embodiment 68

The composition of Embodiment 67 wherein component (c) consistsessentially of one or more poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol)copolymers.

Embodiment 69

The composition of Embodiment 67 or 68 wherein thepoly(lactide-co-glycolide) (or acrylate/methacrylate-based) chain have ahydrophobic chain with an average molecular weight of at least about1,000 daltons.

Embodiment 70

The composition of Embodiment 69 wherein the hydrophobicpoly(lactide-co-glycolide) (or acrylate/methacrylate-based) chain has anaverage molecular weight of at least about 1,200 daltons.

Embodiment 71

The composition of Embodiment 70 wherein the hydrophobicpoly(lactide-co-glycolide) (or acrylate/methacrylate-based) chain has anaverage molecular weight of at least about 1,700 daltons.

Embodiment 72

The composition of Embodiment 71 wherein the hydrophobicpoly(lactide-co-glycolide) (or acrylate/methacrylate-based) chain has anaverage molecular weight of at least about 2,000 daltons.

Embodiment 73

The composition of any one of Embodiments 67 through 72 wherein thepoly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymers have a hydrophobicpoly(lactide-co-glycolide) (or acrylate/methacrylate-based) chain withan average molecular weight of not more than about 5,000 daltons.

Embodiment 74

The composition of Embodiment 73 wherein the hydrophobicpoly(lactide-co-glycolide) (or acrylate/methacrylate-based) chain has anaverage molecular weight of not more than about 4,000 daltons.

Embodiment 75

The composition of Embodiment 74 wherein the hydrophobicpoly(lactide-co-glycolide) (or acrylate/methacrylate-based) chain has anaverage molecular weight of not more than about 3,000 daltons.

Embodiment 76

The composition of any one of Embodiments 64 through 75 wherein thepoly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymers have a hydrophilic content of at leastabout 5% by weight.

Embodiment 77

The composition of Embodiment 76 wherein the hydrophilic content is atleast about 15% by weight.

Embodiment 78

The composition of Embodiment 77 wherein the hydrophilic content is atleast about 20% by weight.

Embodiment 79

The composition of Embodiment 78 wherein the hydrophilic content is atleast about 25% by weight.

Embodiment 80

The composition of Embodiment 79 wherein the hydrophilic content is atleast about 35% by weight.

Embodiment 81

The composition of Embodiment 80 wherein the hydrophilic content is atleast about 45% by weight.

Embodiment 82

The composition of Embodiment 81 wherein the hydrophilic content is atleast about 55% by weight.

Embodiment 83

The composition of Embodiment 82 wherein the hydrophilic content is atleast about 65% by weight.

Embodiment 84

The composition of Embodiment 83 wherein the hydrophilic content is atleast about 75% by weight.

Embodiment 85

The composition of any one of Embodiments 64 through 84 whereinpoly(lactide-co-glycolide) (or acrylate/methacrylate-based)/methylatedpoly(ethylene glycol) copolymers have a hydrophilic content of not morethan about 99% by weight.

Embodiment 86

The composition of Embodiment 85 wherein the hydrophilic content is notmore than about 10% by weight.

Embodiment 87

The composition of Embodiment 86 wherein component (d) comprises one ormore biologically active agents other than anthranilic diamideinsecticides and is at least 0.1% of the composition by weight.

Embodiment 88

The composition of Embodiment 87 wherein component (d) is at least 1% ofthe composition by weight.

Embodiment 89

The composition of any one of Embodiments 86 through 88 whereincomponent (d) is not more than about 60% of the composition by weight.

Embodiment 90

The composition of Embodiment 89 wherein component (d) is not more thanabout 20% of the composition by weight.

Embodiment 91

The composition of any one of Embodiments 86 through 90 whereincomponent (d) comprises at least one fungicide or insecticide (otherthan anthranilic diamide insecticides).

Embodiment 92

The composition of Embodiment 91 wherein component (d) comprises atleast one insecticide.

Embodiment 93

The composition of Embodiment 91 or 92 wherein component (d) comprisesat least one fungicide.

Embodiment 94

The composition of any one of Embodiments 1 through 90 wherein thecomposition does not comprise a biologically active agent other thancomponent (a).

Embodiment 95

The composition of any one of Embodiments 1 through 94 wherein thecomposition further comprises (e) up to about 80% by weight of one ormore inert formulating ingredients other than poly(lactide-co-glycolide)(or acrylate/methacrylate-based)/methylated poly(ethylene glycol)copolymers.

Embodiment 96

The composition of Embodiment 95 wherein component (e) (i.e., the one ormore inert formulating ingredients other than poly(lactide-co-glycolide)(or acrylate/methacrylate-based)/methylated poly(ethylene glycol)copolymers) is at least about 0.1% of the composition by weight.

Embodiment 97

The composition of Embodiment 95 or 96 wherein component (e) is not morethan about 20% of the composition by weight.

Embodiment 98

The composition of any one of Embodiments 95 through 97 whereincomponent (e) comprises at least one inert formulating ingredientselected from the group consisting of adhesives, liquid diluents, soliddiluents, surfactants, antifreeze agents, preservatives, thickeningagents and fertilizers.

Embodiment 99

The geotropic propagule described in the Summary of the Invention whichis coated with an insecticidally effective amount of the composition ofany one of Embodiments 1 through 98.

Embodiment 100

The geotropic propagule of Embodiment 99 which is a seed.

Embodiment 101

The seed of Embodiment 100 which is a seed of cotton, maize, soybean,rapeseed or rice.

Embodiment 102

The seed of Embodiment 101 which is a seed of maize or rapeseed.

Embodiment 103

The seed of Embodiment 102 which is a seed of maize.

Embodiment 104

The seed of Embodiment 102 which is a seed of rapeseed.

Embodiment 105

The liquid composition described in the Summary of the Inventionconsisting of about 5 to 80 weight % of the composition of any one ofEmbodiments 1 through 98 and about 20 to 95 weight % of a volatileaqueous liquid carrier.

Embodiment 106

The liquid composition of Embodiment 105 wherein the volatile aqueousliquid carrier is at least about 25% of the composition by weight.

Embodiment 107

The liquid composition of Embodiment 106 wherein the volatile aqueousliquid carrier is at least about 30% of the composition by weight.

Embodiment 108

The liquid composition of any one of Embodiments 105 through 107 whereinthe aqueous liquid carrier is not more than about 70% of the compositionby weight.

Embodiment 109

The liquid composition of any one of Embodiments 105 through 107 whereinthe volatile aqueous liquid carrier comprises at least about 80% waterby weight.

Embodiment 110

The liquid composition of Embodiment 109 wherein the volatile aqueousliquid carrier comprises at least about 90% water by weight.

Embodiment 111

The liquid composition of Embodiment 110 wherein the volatile aqueousliquid carrier comprises at least about 95% water by weight.

Embodiment 112

The liquid composition of Embodiment 111 wherein the volatile aqueousliquid carrier consists essentially of water.

Embodiment 113

The liquid composition of Embodiment 112 wherein the volatile aqueousliquid carrier is water.

Embodiment 114

The liquid composition of any one of Embodiments 105 through 113 whereinat least some of component (a) is present in the liquid composition assolid particles.

Embodiment 115

The liquid composition of Embodiment 114 wherein at least about 90% ofcomponent (a) is present in the composition as solid particles.

Embodiment 116

The liquid composition of Embodiment 115 wherein at least about 95% ofcomponent (a) is present in the composition as solid particles.

Embodiment 117

The liquid composition of Embodiment 116 wherein at least about 98% ofcomponent (a) is present in the composition as solid particles.

Embodiment 118

The liquid composition of any one of Embodiments 114 through 117 whereinmore than 95% by weight of the particles have a particle size less thanabout 300 nm.

Embodiment 119

The liquid composition of any one of Embodiments 114 through 118 whereinthe median particle size of the particles is not more than about 300 nm.

Embodiment 120

The liquid composition of Embodiment 118 or 119 wherein the medianparticle size of the particles is not more than about 200 nm.

Embodiment 121

The liquid composition of Embodiment 120 wherein the median particlesize of the particles is not more than about 150 nm.

Embodiment 122

The liquid composition of Embodiment 121 wherein the median particlesize of the particles in not more than about 125 nm.

Embodiment 123

The liquid composition of Embodiment 122 wherein the median particlesize of the particles is not more than about 110 nm.

Embodiment 124

The liquid composition of any one of Embodiments 114 through 123 whereinthe median particle size of the particles is at least about 100 nm.

Embodiment 125

The method described in the Summary of the Invention for protecting ageotropic propagule and plant derived therefrom from a phytophagousinsect pest, the method comprising coating the propagule with aninsecticidally effective amount of the liquid composition of any one ofEmbodiments 105 through 124 and then evaporating the volatile aqueousliquid carrier.

Embodiment 126

The method of Embodiment 125 wherein the insect pest is in a taxonomicorder selected from Hemiptera and Lepidoptera.

Embodiment 127

The method of Embodiment 126 wherein the insect pest is in a taxonomicfamily selected from Aleyrodidae, Aphidadae, Cicadellidae, Delphacidae,Gelechiidae, Lymantriidae, Noctuidae, Plutellidae, Pyralidae andTorticidae.

Embodiment 128

The method of Embodiment 127 wherein the insect pest is in the familyNoctuidae.

Embodiment 129

The composition of any one of Embodiments 1 through 98, wherein thepolylactic acid (b) comprises at least one polymer of Formula 2 orFormula 5

where each R₁ is independently selected from H and CH₃; and X is aninteger of from 5 to 50, inclusive;

where each R₄ is independently selected from H and CH₃; and Y areindependently selected from integers from 10 to 100 and Q can be benzyl,glycidyl, C₁-C₂₀ straight chain alkyl, (e.g., methyl, ethyl, n-butyl,hexadecyl, octadecyl, lauryl, stearyl), C₃-C₂₀ branched alkyl (e.g.,isodecyl, isooctyl, isotridecyl, tert-butyl), 2-phenoxyethyl, isobornylor tetrahydro furfuryl, hydroxyethyl or 3-hydroxy propyl. Q can also bea functional group derived from the reaction of a glycidyl group withcysteine, tryptophan, dihydroxyphenylalanine, phenylalanine, lysine,histidine, arginine, asparagine, glutamine, diethylene glycol,triethylene glycol, tetraethylene glycol, or 1,6-hexanediol; and whereinthe poly(lactide-co-glycolide) (oracrylate/methacrylate-based)/methylated poly(ethylene glycol) copolymers(c) comprises at least one polymer of Formula 7

where m varies independently from 2 to 200 and suitable Z groups fromZ¹-Z² are shown below:

where k varies independently from 2 to 200.

Embodiments of this invention can be combined in any manner. An exampleof such combination is the insecticidal composition described in theSummary of the Invention comprising by weight (a) from about 0.25 toabout 2.5% of one or more anthranilic diamide insecticides; and (b) fromabout 2.5 to about 25% of apolylactic acid polymer component having awater solubility of at least about 5% by weight at 20° C., an HLB valueranging from about 3 to about 31 and an average molecular weight rangingfrom about 700 to about 4,000 daltons; wherein the ratio of component(b) to component (a) is about 1:1 to about 1:10 by weight; and fromabout 20 to about 50% of a poly(lactide-co-glycolide)(oracrylate/methacrylate-based polymer)/methyl poly(ethylene glycol)copolymer having a water solubility of at least about 5% by weight at20° C., a hydrophilic-lipophilic balance value of at least about 7, andan average molecular weight ranging from 12,000 to 65,000 wherein theratio of poly(lactide-co-glycolide) or acrylate/methacrylate-based

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative and not limiting of the disclosure in any waywhatsoever.

EXAMPLES

Table 1 describes the nanoparticles comprised of polymer/anthanilamidecompositions used in the Examples and Comparative Examples. Allnanoparticles comprised of polymer/anthanilamide compositions weresynthesized as described below. Molecular weight and HLB values for thenanoparticles comprised of polymer/anthanilamide compositions weredetermined by size exclusion chromatography (SEC).

TABLE 1 Identity of Nanoparticles Comprised of Polymer/AnthanilamideCompositions Abbreviated MW Name Formula 2 Formula 7 (daltons) HLB1-NP665 none Z₁ = —(OCH₂CH₂)₂₅—OCH₃ 14,600 18 Z₂ = —(OC(CH₃)COOCH₂CO)—2-NP665 R₁ = CH₃ Z₁ = —(OCH₂CH₂)₂₅—OCH₃ 15,400 14 Z₂ =—(OC(CH₃)COOCH₂CO)— 3-NP665 R₁ = CH₃ Z₁ = —(OCH₂CH₂)₂₅—OCH₃ 16,290 14 Z₂= —(OC(CH₃)COOCH₂CO)—

PCT Patent Publication WO 2006/062978 discloses methods for preparing3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)-carbonyl]phenyl]-1H-pyrazole-5-carboxamide(i.e., Compound 1). Example 15 of this publication discloses preparationof Compound 1 as a powder melting at 177-181° C. (with apparentdecomposition), which is a crystal form that is readily hydrated.Example 15 also discloses recrystallization from 1-propanol to providecrystals melting at 217-219° C., which is an anhydrous crystal form thatis resistant to hydration. The samples of Compound 1 used in the presentExamples and Comparative Examples were assayed to contain about 94-98%by weight of Compound 1, which is believed to be a mixture of these twocrystal forms.

PCT Patent Publication WO 03/015519 discloses methods for preparing3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide(i.e., Compound 2). Example 7 of this publication discloses preparationof Compound 2 as a powder melting at 239-240° C. The samples of Compound2 used in the present Examples and Comparative Examples were assayed tocontain about 96-97% by weight of Compound 2.

The weight percentages of Compound 1 or 2 reported in the presentExamples refer to the amount of Compound 1 or 2 contained in thetechnical material used; the other constituents in the technicalmaterial are not separately listed, but when added to weight percentagesof the listed composition components result in a total of about 100%.

General Procedure for Coating Seeds

A fluidized bed system was used for coating seeds with the compositionsdescribed in the following examples. Seeds were tossed by verticalstreams of hot air while being sprayed with the aqueous composition. Thehot air evaporated the water carrier from the composition applied to theseeds. The amount of composition introduced into the coating system wasadjusted to compensate for material lost exiting the coater or coatingareas other than the seeds, so as to deliver the stated targetapplication rate to the seeds.

General Procedure for Assaying Anthranilic Diamide Concentration inLeaves

Plant leaves were macerated using a Geno/Grinder 2000 bead beaterhomogenizer (SPEX CertiPrep, Metuchen, N.J., USA), and then acetonitrile(˜5 mL/g of leaf tissue) was added. The mixture was further shaken for 1minute using the Geno/Grinder homogenizer, and then centrifuged. Theacetonitrile extract supernatant was analyzed by high performance liquidchromatography with tandem mass spectrometry detection (HPLC/MS/MS)using a Waters (Milford, Mass. USA) Alliance HT2795 chromatograph andZorbax SB C18 (2.1×50 mm, 5 micron) column eluted with mixtures of waterand acetonitrile containing 0.1% (volume/volume) of formic acid, withdetection by a Waters Quattro Micro API Mass Spectrometer usingelectrospray ionization (ESI+). Standard solutions of Compound 1 andCompound 2 were prepared by adding measured amounts of stock solutionsof Compound 1 or Compound 2 in acetonitrile or tetrahydrofuran toacetonitrile extracts of leaves from plants grown from untreated seeds.

In a laboratory test involving 2nd instar larva of Spodoptera frugiperdaon maize leaves, a concentration of 0.033 micrograms of Compound 2 per gof leaf tissue resulted in 50% mortality within 72 h, and aconcentration of 0.037 micrograms per g of tissue was needed to achieve100% mortality within 72 h.

Examples 1-3 Synthesis and Purification

Synthesis of Polymerization Catalyst

A flask of BDI-3(0.00125 mol, 0.0523 g) was dissolved in toluene (5 mL)in a nitrogen atmosphere box. Zinc(bis(trimethylsilyl)amide (0.00125mol, 0.505 mL) was added to the solution. The solution was stirred for18 hours at 80° C. The clear yellow solution was dried under vacuum.

Hydrogenation of Anthranilic Diamides

H_(2(g)) was added to cyantraniliprole (0.02 mol) over a palladiumalumina catalyst under 3 atm of pressure. The white powder was collectedand dried under vacuum for 4 hrs.

Synthesis of Methylated Poly(Ethylene Glycol)-(Lactic-Co-Glycolic Acid)Block Copolymer (mPEG-PLGA)

Glass tubes were dried in an oven set at 200° C. for 12 hours. Driedtubing was charged with glycolide (0.003 mol, 0.228 g), lactic acid(0.01 mol, 1.44 g) and mPEG (M.W. 4000, 0.52 g). Stannous octoate (0.6mg, dissolved in hexane) was added to the tube. The tube was put into avacuum oven (VWR 1410) at 190° C. for 3 hours. Upon reaction completionthe solution was dissolved in chloroform (10 mL) and precipitated intoexcess (5:1) methanol. The polymers were died under vacuum for 12 hrs.

Anthranilic Diamide-Poly(Lactic Acid) Nanoconjugates

Anthranilic diamide (0.01 mol) and [(BDI)ZnN(SiMe₃)₂] (0.01 mol) werestirred at room temperature in anhydrous THF (5 mL). Lactide (1 mmol)was dissolved in anhydrous THF (2 mL) and added dropwise to thesolution. Upon reaction completion, the polymerization solution wasadded to ethyl ether (25 mL) and the cyantraniliprole-poly(lactic acid)conjugates precipitated out of solution. The anthranilicdiamide-poly(lactic acid) conjugates were re-dissolved in DMF (1 mL) andadded dropwise to vigorously stirred Millipore water (2 mL). This causedprecipitation of the anthranilic diamide-poly(lactic acid) conjugates.mPEG-PLGA (5 mg/mL) was dissolved in DMF (1 mL) and added dropwise tothe anthranilic diamide-PLA conjugates resulting in PEGylatedanthranilic diamide-poly(lactic acid) conjugates. Descriptions of theanthranilic diamide-poly(lactic acid) nanoconjugates synthesized areshown in Table 2.

TABLE 2 Synthesis of poly(lactide-co-glycolide) or(acrylate/methacrylate- based)/methylated poly(ethylene glycol) triblockcopolymers Abbreviated Initiator Monomer 1 Monomer 2 MW Name (moles)(moles) (moles) (daltons) 1-NP665 0.01 0 100 14,600 2-NP665 0.01 10 10015,400 3-NP665 0.01 10 100 16,290

Examples 1-3 and Comparative Example A Description of Examples fromCanola Greenhouse Trials General Procedure for Preparing InsecticidalCompositions

The compositions of Examples 1-3 and Comparative Example A were mixedwith a 1:3 by weight mixture of the fungicide products MAXIM 4FS (40.3%fludioxonil, syngenta AG) and APRON XL (33.3% mefenoxam, Syngenta AG),and (2) the colorant Acid Blue Dye, and then the resultant compositionswere used to coat canola seeds at an application rate of 0.6 g ofCompound 1, 0.067 mL of the fungicide mixture (1A) and 0.033 g of thecolorant (2) per 100 g of canola seeds (100 g corresponding to about23,400 seeds for Examples 1-3, and Comparative Example A). (“Canola” isa cultivar of the rapeseed species Brassica napus L. that produces anedible oil.)

For Comparative Example A, 1.01 g of Compound 1 was dissolved in 50 mLof 30 wt % ethanol/methylene chloride. The solvent was removed by rotaryevaporation. Some of the residue (0.5 g) was mixed with 1 g of water forseed coating.

The coated canola seeds were then evaluated for ability to provideCompound 1 to leaves developing from the seeds. Each treatment involvedfour pots to provide quadruple replication. Four coated canola seedswere planted in sterile Matapeake sand blend soil in each pot and thengrown in a growth chamber (25° C., 18 h light, 6 h dark) for 18-20 days.Three plants in each pot were selected for sampling. From each of thethree plants, the second leaf was cut at the stem. All three leavescollected from each pot were placed into one vial and then analyzedaccording to the general procedure described above for assayinganthranilic diamide concentration in leaves. The concentrations measuredfrom leaves in each of the four pots (total of 12 leaves) were averagedto provide the values reported in Table 3.

TABLE 3 Uptake of Compound 1 in Canola Compo- MW Uptake Normalized nent(dal- ug/g of Improvement vs (b) tons) HLB leaf Compound 1 Example 11-NP665 14,600 18 0.065 5.9 2 2-NP665 15,400 14 0.048 4.4 3 3-NP66516,290 14 0.046 4.2 Comparative Example A Com- NA 0.011 1 pound 1

What is claimed is:
 1. An insecticidal composition comprising by weightbased on the total weight of the composition: (a) from about 0.25 toabout 25% of one or more anthranilic diamide insecticides; (b) fromabout 2.5 to about 25% of a poly(lactic acid) polymer component having awater dispersabilitiy of at least about 5% by weight at 20° C. and anaverage molecular weight ranging from about 700 to about 4,000 daltons;wherein the ratio of component (b) to component (a) is about 1:1 toabout 1:10 by weight; and (c) from about 20 to about 50% of acomposition comprising either (i) a poly(lactide-co-glycolide) copolymerand a methyl poly(ethylene glycol) copolymer, or (ii) anacrylate/methacrylate-based polymer or copolymer and a methylpoly(ethylene glycol) copolymer, wherein the methyl poly(ethyleneglycol) copolymer has a water solubility of at least about 5% by weightat 20° C., a hydrophilic-lipophilic balance value of at least about 7,and an average molecular weight ranging from 12,000 to 65,000, andfurther wherein the ratio of the poly(lactide-co-glycolide) or theacrylate/methacrylate-based polymer or copolymer, to the methylpoly(ethylene glycol) is about 1:1 to about 4:1 by weight and the ratioof component (c) to component (b) is about 2:1 to about 9:1 by weight.2. The composition of claim 1, wherein component (a) comprises at leastone compound selected from anthranilic diamides of Formula 1, N-oxides,and salts thereof,

wherein X is N, CF, CCl, CBr or Cl; R¹ is CH₃, Cl, Br or F; R² is H, F,Cl, Br or —CN; R³ is F, Cl, Br, C₁-C₄ haloalkyl or C₁-C₄ haloalkoxy;R^(4a) is H, C₁-C₄ alkyl, cyclopropylmethyl or 1-cyclopropylethyl;R^(4b) is H or CH₃; R⁵ is H, F, Cl or Br; and R⁶ is H, F, Cl or Br. 3.The composition of claim 2, wherein component (a) is selected fromcompounds of Formula 1 wherein X is N; R¹ is CH₃; R² is Cl or —CN; R³ isBr; R^(4a) is CH₃; R^(4b) is H; R⁵ is Cl; and R⁶ is H; and saltsthereof.
 4. The composition of claim 3, wherein component (a) is thecompound of Formula 1 wherein R² is Cl.
 5. The composition of claim 3,wherein component (a) is the compound of Formula 1 wherein R² is —CN. 6.The composition of claim 1, wherein component (b) is at least about 15%of the composition by weight.
 7. The composition of claim 1 whereincomponent (b) is a polylactic acid polymer of Formula 2,

where each R₁ is independently selected from H and CH₃; and X is aninteger of from 5 to
 50. 8. The composition of claim 1, wherein theratio of component (c) to component (b) is at least about 2:1 by weight.9. The composition of claim 1 wherein the methyl poly(ethylene glycol)copolymer has a structure according to Formula 7,

wherein m is an integer between 2 to 200, inclusive and Z is Z¹ or Z²shown below:

where p and k each vary independently from 2 to 200, inclusive.
 10. Thecomposition of claim 1, further comprising at least one fungicide orinsecticide other than anthranilic diamide insecticides.
 11. A geotropicpropagule coated with an insecticidally effective amount of thecomposition of claim
 1. 12. The geotropic propagule of claim 11, whereinthe geotropic propagule is a seed.
 13. The geotropic propagule of claim12, wherein the seed is a seed of cotton, maize, soybean, rapeseed orrice.
 14. A liquid composition consisting of about 5 to 80 weight % ofthe composition of claim 1 and about 20 to 95 weight % of a volatileaqueous liquid carrier.
 15. A method for protecting a geotropicpropagule and plant derived therefrom from a phytophagous insect pest,the method comprising coating the propagule with an insecticidallyeffective amount of the liquid composition of claim 14 and thenevaporating the volatile aqueous liquid carrier of the composition. 16.The method of claim 15 wherein the insect pest is in a taxonomic orderselected from Hemiptera and Lepidoptera.